WO2019150833A1

WO2019150833A1 - Composition, film, infrared-transmitting filter, and solid imaging element

Info

Publication number: WO2019150833A1
Application number: PCT/JP2018/047133
Authority: WO
Inventors: 全弘森
Original assignee: 富士フイルム株式会社
Priority date: 2018-02-02
Filing date: 2018-12-21
Publication date: 2019-08-08
Also published as: US20200299512A1; TWI788500B; JPWO2019150833A1; TW201934670A; US11920041B2

Abstract

Provided are: a composition capable of forming a film having excellent light resistance; a film having excellent light resistance; an infrared-transmitting filter; and a solid imaging element. The composition comprises a metal-free phthalocyanine compound, a red colorant, and a solvent, the ratio of the absorbance A at a wavelength of 700 nm to the absorbance B at a wavelength of 810 nm, A/B, being 10 or greater.

Description

Composition, film, infrared transmission filter, and solid-state imaging device

The present invention relates to a composition containing a metal-free phthalocyanine compound. The present invention also relates to a film, an infrared transmission filter, and a solid-state imaging device using the above-described composition.

Solid-state image sensors are used as optical sensors for various purposes. For example, infrared rays have a wavelength longer than that of visible light, so that they are not easily scattered, and can be used for distance measurement, three-dimensional measurement, and the like. Infrared rays are invisible to humans and animals, so even if you illuminate the subject with infrared rays at night, the subject will not be noticed. It can also be used for shooting. As described above, an optical sensor (infrared sensor) that detects infrared rays can be used in various applications. In the infrared sensor, an infrared transmission filter or the like is used. The infrared transmission filter is manufactured using a composition containing a color material (see, for example, Patent Document 1).

On the other hand, Patent Document 2 discloses a black matrix coloring composition in which two or more organic pigments selected from five organic pigments of blue, purple, yellow, red, and orange are combined and pseudo-blackened. The organic pigment is C.I. I. Pigment blue 16, C.I. I. Pigment blue 79, C.I. I. Pigment violet 29, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 176, C.I. I. Pigment yellow 185, and C.I. I. An invention relating to a black matrix coloring composition containing at least one selected from the group consisting of CI Pigment Yellow 213 is described.

Japanese Patent Laid-Open No. 2016-177079 JP 2014-228780 A

A film manufactured using a composition containing a coloring material may change its spectral characteristics due to long-term light irradiation. In particular, since the infrared transmission filter may contain a relatively large amount of color material, the spectral characteristics tend to vary more easily due to long-term light irradiation. On the other hand, in order to maintain various performances of the solid-state imaging device over a long period of time, further improvement in light resistance is desired for infrared transmission filters and the like.

Further, when the present inventors examined the films described in Patent Documents 1 and 2, it was found that these films have insufficient light resistance and there is room for further improvement.

Therefore, an object of the present invention is to provide a composition capable of forming a film having excellent light resistance. Another object of the present invention is to provide a film having excellent light resistance, an infrared transmission filter, and a solid-state imaging device.

Under such circumstances, as a result of intensive studies by the inventor, the present inventors have found that the above object can be achieved by adopting the configuration described later, and have completed the present invention. Accordingly, the present invention provides the following.
<1> A composition comprising a metal-free phthalocyanine compound, a red colorant, and a solvent, wherein the ratio A / B of the absorbance A at a wavelength of 700 nm and the absorbance B at a wavelength of 810 nm is 10 or more.
<2> The composition according to <1>, wherein the metal-free phthalocyanine compound is a blue colorant.
<3> The composition according to <1> or <2>, wherein the metal-free phthalocyanine compound is Color Index Pigment Blue 16.
<4> The composition according to any one of <1> to <3>, further comprising at least one selected from a yellow colorant and a purple colorant.
<5> The ratio C / D between the minimum absorbance C in the wavelength range of 400 to 700 nm and the maximum absorbance D in the wavelength range of 810 to 1100 nm is 4.5 or more, <1> to <4> The composition according to any one of the above.
<6> The composition according to any one of <1> to <5>, which is for an infrared transmission filter.
<7> A film obtained using the composition according to any one of <1> to <6>.
<8> An infrared transmission filter having the film according to <7>.
<9> A solid-state imaging device having the infrared transmission filter according to <8>.
<10> The solid-state imaging device according to <9>, further including a band-pass filter that transmits at least part of infrared light transmitted by the infrared transmission filter on an optical path of the infrared transmission filter.
<11> The solid-state imaging device according to <10>, wherein the band-pass filter is a filter that transmits visible light and at least a part of infrared rays transmitted by the infrared transmission filter.
<12> The bandpass filter has a maximum transmittance of 10% or less in a wavelength range of 730 to 780 nm and a minimum transmittance of 70% or more in a wavelength range of 840 to 860 nm, <10> or <11> The solid-state imaging device according to <11>.
<13> In the wavelength range of 700 to 850 nm, the wavelength λ1 at which the transmittance of the infrared transmission filter is 50% is shorter than the shortest wavelength λ2 at which the transmittance of the bandpass filter is 50%, and the wavelength λ2 The solid-state imaging device according to any one of <10> to <12>, wherein a difference from the wavelength λ1 is 30 nm or more.

According to the present invention, a composition capable of forming a film having excellent light resistance can be provided. In addition, a film having excellent light resistance, an infrared transmission filter, and a solid-state imaging device can be provided.

It is a figure which shows one Embodiment of the solid-state image sensor of this invention.

Hereinafter, the contents of the present invention will be described in detail.
In the present specification, “˜” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In the notation of a group (atomic group) in the present specification, the notation in which neither substitution nor substitution is described includes a group (atomic group) having a substituent together with a group (atomic group) having no substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, unless otherwise specified, “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. Examples of the light used for exposure include an emission line spectrum of a mercury lamp, actinic rays or radiation such as far ultraviolet rays, extreme ultraviolet rays (EUV light) typified by excimer laser, X-rays, and electron beams.
In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, and “(meth) acryl” represents both and / or acrylic and “(meth) acrylic”. ) "Acryloyl" represents both and / or acryloyl and methacryloyl.
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value in gel permeation chromatography (GPC) measurement.
In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220GPC (manufactured by Tosoh Corporation), and as columns, TOSOH TSKgel Super HZM-H and TOSOH TSKgel Super HZ4000 It can be determined by using a column connected with TOSOH TSKgel Super HZ2000 and using tetrahydrofuran as a developing solvent.
In this specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In this specification, “infrared rays” refers to light (electromagnetic waves) having a wavelength of 700 to 2500 nm.
In the present specification, “total solid content” refers to the total mass of components excluding the solvent from all components of the composition.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .

<Composition>
The composition of the present invention comprises a metal-free phthalocyanine compound, a red colorant, and a solvent, and a ratio A / B of absorbance A at a wavelength of 700 nm and absorbance B at a wavelength of 810 nm is 10 or more. To do. According to the composition of the present invention, a film excellent in light resistance can be produced. The reason why such an effect can be obtained is speculative, but the red colorant and the metal-free phthalocyanine tend to cause the transfer of light energy, and as a result, unnecessary light energy is used for the decomposition reaction of the coloring material. It is presumed that a film that diverges and is excellent in light resistance can be produced. Moreover, since this composition has a ratio A / B of the absorbance A at a wavelength of 700 nm and the absorbance B at a wavelength of 810 nm of 10 or more, it is also possible to produce a film having excellent light transmittance exceeding a wavelength of 810 nm. .

In the composition of the present invention, the ratio A / B between the absorbance A at a wavelength of 700 nm and the absorbance B at a wavelength of 810 nm is 10 or more, preferably 15 or more, more preferably 20 or more, more preferably 25 or more. More preferably. The upper limit can be 100 or less. When the absorbance ratio is 10 or more, it is possible to form a film having excellent light transmittance exceeding a wavelength of 810 nm.

The ratio C / D between the minimum absorbance C in the wavelength range of 400 to 700 nm and the maximum absorbance D in the wavelength range of 810 to 1100 nm of the composition of the present invention is 4.5 or more, 7.5 or more. Preferably, it is 15 or more, more preferably 30 or more. When the absorbance ratio is 4.5 or more, it is possible to form a film that has high light blocking properties for light with a wavelength of 400 to 700 nm and excellent light transmittance for light with a wavelength of 810 nm.

The absorbance Aλ at a certain wavelength λ is defined by the following equation (1).
Aλ = −log (Tλ / 100) (1)
Aλ is the absorbance at the wavelength λ, and Tλ is the transmittance (%) at the wavelength λ.
In the present invention, the absorbance value may be a value measured in the state of a solution, or may be a value of a film formed using the composition. When measuring the absorbance in the state of the film, the composition is applied on the glass substrate by a method such as spin coating so that the thickness of the film after drying becomes a predetermined thickness, and 100 ° C. using a hot plate. It is preferable to measure using a film prepared by drying for 120 seconds.

The composition of the present invention has a film thickness after drying of 10.0 μm or less (preferably 5.0 μm or less, more preferably 3.0 μm or less, still more preferably 2.5 μm or less, even more preferably. Is not more than 2.0 μm, particularly preferably not more than 1.5 μm, and the lower limit can be not less than 0.4 μm, can be not less than 0.5 μm, and can be not less than 0.6 μm. At least 0.7 μm, 0.8 μm or more, or 0.9 μm or more). In one, the transmittance of light having a wavelength of 700 nm is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less. Further, in at least one of the aforementioned film thicknesses, the transmittance of light having a wavelength of 810 nm is preferably 70% or more, more preferably 75% or more, and further preferably 80% or more. In at least one of the aforementioned film thicknesses, the maximum value of the transmittance of light having a wavelength of 400 to 700 nm is preferably 20% or less, more preferably 15% or less, and further preferably 10% or less. preferable. Further, the minimum transmittance of light having a wavelength of 810 to 1100 nm is preferably 70% or more, more preferably 75% or more, and further preferably 80% or more.

Since the composition of the present invention transmits infrared rays, it can also be said to be an infrared transparent composition. Below, each component which can comprise the composition of this invention is demonstrated.

<< Metal-free phthalocyanine compound >>
The composition of the present invention comprises a metal-free phthalocyanine compound. A metal-free phthalocyanine compound is a phthalocyanine compound having no central metal. The metal-free phthalocyanine compound used in the present invention may be a pigment or a dye. The metal-free phthalocyanine compound used in the present invention is preferably a blue colorant. The metal-free phthalocyanine compound is preferably a compound represented by the following formula (Pc1).

In the formula, R ¹ to R ¹⁶ each independently represents a hydrogen atom or a substituent. Examples of the substituent include a substituent T described later, and are preferably a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthio group, an arylthio group, a heteroarylthio group, and an amino group. An alkylthio group is more preferable, and a halogen atom is more preferable.

Preferable embodiments of the metal-free phthalocyanine compound include the following (1) to (3), and (1) is preferable because the effects of the present invention are more easily obtained. Also, the smaller the substituent, the more advantageous the formulation design, such as the easier absorption slope on the shorter wavelength side and the easier adjustment of the spectral characteristics of the composition.
(1) Embodiment in which all of R ¹ to R ¹⁶ are hydrogen atoms (2) Embodiment in which all of R ¹ to R ¹⁶ are substituents (3) 1-3 of R ¹ to R ⁴ are substituents 1 to 3 of R ⁵ to R ⁸ are substituents, 1 to 3 of R ⁹ to R ¹² are substituents, and 1 to 3 of R ¹³ to R ¹⁶ are substituents. The aspect which is

(Substituent T)
Examples of the substituent T include the following groups. An alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), an alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), an alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), an aryl group (preferably An aryl group having 6 to 30 carbon atoms), an amino group (preferably an amino group having 0 to 30 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms), an aryloxy group (preferably having 6 to 6 carbon atoms). 30 aryloxy groups), heteroaryloxy groups, acyl groups (preferably acyl groups having 1 to 30 carbon atoms), alkoxycarbonyl groups (preferably alkoxycarbonyl groups having 2 to 30 carbon atoms), aryloxycarbonyl groups (preferably Is an aryloxycarbonyl group having 7 to 30 carbon atoms), a heteroaryloxycarbonyl group, an acyloxy group ( Preferably an acyloxy group having 2 to 30 carbon atoms), an acylamino group (preferably an acylamino group having 2 to 30 carbon atoms), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms), an aryloxycarbonyl An amino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms), a sulfamoyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms), a carbamoyl group (preferably a carbamoyl group having 1 to 30 carbon atoms), an alkylthio group (Preferably an alkylthio group having 1 to 30 carbon atoms), an arylthio group (preferably an arylthio group having 6 to 30 carbon atoms), a heteroarylthio group (preferably 1 to 30 carbon atoms), an alkylsulfonyl group (preferably a carbon number) 1-30), arylsulfonyl groups (preferably charcoal) 6-30), heteroarylsulfonyl group (preferably 1-30 carbon atoms), alkylsulfinyl group (preferably 1-30 carbon atoms), arylsulfinyl group (preferably 6-30 carbon atoms), heteroarylsulfinyl group (Preferably 1 to 30 carbon atoms), ureido group (preferably 1 to 30 carbon atoms), hydroxy group, carboxyl group, sulfo group, phosphoric acid group, carboxylic acid amide group, sulfonic acid amide group, imido acid group, mercapto Group, halogen atom, cyano group, alkylsulfino group, arylsulfino group, hydrazino group, imino group, heteroaryl group (preferably having 1 to 30 carbon atoms). When these groups are further substitutable groups, they may further have a substituent. Examples of the further substituent include the groups described for the substituent T described above.

Specific examples of the metal-free phthalocyanine compound include compounds having the following structure, and Color Index Pigment Blue 16 is preferable because the effects of the present invention are easily obtained. In the following structural formulas, Me represents a methyl group, and Ph represents a phenyl group. PB16 is color index pigment blue 16.

The content of the metal-free phthalocyanine compound is preferably 5 to 40% by mass with respect to the total solid content of the composition of the present invention. The lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more. The upper limit is preferably 30% by mass or less, and more preferably 25% by mass or less.

<< red colorant >>
The composition of the present invention includes a red colorant. Examples of the red colorant include a diketopyrrolopyrrole compound, an anthraquinone compound, an azo compound, a quinacridone compound, a perylene compound, and the like, and a diketopyrrolopyrrole compound is preferable because it is easy to obtain better light resistance. Although details are not clear, it is estimated that the diketopyrrolopyrrole compound has higher crystallinity, and therefore energy transfer is more likely to occur. For this reason, more excellent light resistance is obtained by using a diketopyrrolopyrrole compound as a red colorant. The red colorant may be a pigment or a dye.

As the red pigment, Color Index (CI) Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172 , 175,176,177,178,179,184,185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255 , 264 270,272,279, and the like, C. I. Pigment Red 254 and 264 are preferable.

Further, as the red pigment, a compound having a structure in which an aromatic ring group in which a group in which an oxygen atom, a sulfur atom, or a nitrogen atom is bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton can be used. As such a compound, a compound represented by the formula (DPP1) is preferable, and a compound represented by the formula (DPP2) is more preferable.

In the above formula, R ¹¹ and R ¹³ each independently represent a substituent, R ¹² and R ¹⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, and n11 and n13 each independently And X ¹² and X ¹⁴ each independently represents an oxygen atom, a sulfur atom or a nitrogen atom, and when X ¹² is an oxygen atom or a sulfur atom, m12 represents 1, If ¹² is a nitrogen atom, m12 represents 2, if X ¹⁴ is an oxygen atom or a sulfur atom, m14 represents 1, if X ¹⁴ is a nitrogen atom, m14 represents 2. Examples of the substituent represented by R ¹¹ and R ¹³ include the groups described above for the substituent T, and include an alkyl group, an aryl group, a halogen atom, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and a heteroaryloxycarbonyl group. Preferred examples include a group, an amide group, a cyano group, a nitro group, a trifluoromethyl group, a sulfoxide group, and a sulfo group.

The content of the red colorant is preferably 5 to 40% by mass with respect to the total solid content of the composition of the present invention. The lower limit is preferably 7% by mass or more, and more preferably 10% by mass or more. The upper limit is preferably 35% by mass or less, and more preferably 30% by mass or less. The content of the red colorant is preferably 50 to 150 parts by mass with respect to 100 parts by mass of the metal-free phthalocyanine compound. The lower limit is preferably 60 parts by mass or more, and more preferably 70 parts by mass or more. The upper limit is preferably 140 parts by mass or less, and more preferably 130 parts by mass or less.

The total content of the metal-free phthalocyanine compound and the red colorant is preferably 20 to 70% by mass with respect to the total solid content of the composition of the present invention. The lower limit is preferably 30% by mass or more, and more preferably 35% by mass or more. The upper limit is preferably 65% by mass or less, and more preferably 60% by mass or less.

(Other color materials)
The composition of the present invention can contain a colorant other than the metal-free phthalocyanine compound and the red colorant. Examples of other colorants include yellow colorants, purple colorants, orange colorants, green colorants, and black colorants. The composition of the present invention preferably contains at least one selected from a yellow colorant and a purple colorant as the other colorant, and more preferably contains a yellow colorant and a purple colorant. According to this aspect, the composition satisfying the spectral characteristics in which the ratio C / D between the minimum absorbance C in the wavelength range of 400 to 700 nm and the maximum absorbance D in the wavelength range of 810 to 1100 nm is 4.5 or more. Easy to prepare. The other coloring material may be a pigment or a dye. The pigment is preferably an organic pigment. The following are mentioned as an organic pigment.

C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175 176,177,179,180,181,182,185,187,188,193,194,199,213,214 like (or more, and yellow pigment),
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (Orange pigment)
C. I. Pigment Green 7, 10, 36, 37, 58, 59, etc. (above, green pigment),
C. I. Pigment violet 1, 19, 23, 27, 32, 37, 42, etc. (above, purple pigment).

The dye is not particularly limited, and a known dye can be used. Further, the dyes described in JP-A-2015-028144 and JP-A-2015-34966 can also be used.

¡As yellow colorant, C.I. I. Pigment Yellow 139, 150, and 185 are preferred, and C.I. I. Pigment Yellow 139 and 150 are more preferable, and C.I. I. Pigment Yellow 139 is more preferable. Examples of purple colorants include C.I. I. Pigment Violet 23 is preferable.

Examples of the black colorant include xanthene compounds, bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds. Examples of the xanthene compound include compounds having the following structure. Examples of the bisbenzofuranone compound include those described in JP-T 2010-534726, JP-T 2012-515233, JP-T 2012-515234, International Publication WO 2014/208348, JP-T 2015-525260, and the like. Examples of such a compound include “Irgaphor Black” manufactured by BASF. Examples of perylene compounds include C.I. I. Pigment Black 31, 32 and the like. Examples of the azomethine compound include those described in JP-A-1-170601, JP-A-2-34664, etc., and can be obtained, for example, as “Chromofine Black A1103” manufactured by Dainichi Seika Co., Ltd.

In the present invention, the bisbenzofuranone compound is preferably a compound represented by the following formula or a mixture thereof.

In the formula, R ¹ and R ² each independently represent a hydrogen atom or a substituent, R ³ and R ⁴ each independently represent a substituent, and a and b each independently represent an integer of 0 to 4 And when a is 2 or more, the plurality of R ³ may be the same or different, the plurality of R ³ may be bonded to form a ring, and b is 2 or more. The plurality of R ⁴ may be the same or different, and the plurality of R ⁴ may be bonded to form a ring. Examples of the substituent represented by R ¹ to R ⁴ include the substituent T described above. For details of the bisbenzofuranone compound, the description in paragraphs 0014 to 0037 of JP-T-2010-534726 can be referred to, and the contents thereof are incorporated herein.

The composition of the present invention comprises, as another colorant, at least one anion selected from an azo compound represented by the following formula (I) and an azo compound having a tautomer structure thereof, two or more metal ions, A metal azo pigment containing a melamine compound can also be used.

In the formula, R ¹ and R ² are each independently OH or NR ⁵ R ⁶ , R ³ and R ⁴ are each independently ═O or ═NR ⁷ , and R ⁵ to R ⁷ are each Independently, it is a hydrogen atom or an alkyl group. The alkyl group represented by R ⁵ to R ⁷ preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear. The alkyl group may have a substituent. Examples of the substituent include the substituent T described above, and a halogen atom, a hydroxy group, an alkoxy group, a cyano group, and an amino group are preferable.

In formula (I), R ¹ and R ² are preferably OH. R ³ and R ⁴ are preferably ═O.

The melamine compound in the metal azo pigment is preferably a compound represented by the following formula (II).

In the formula, R ¹¹ to R ¹³ each independently represents a hydrogen atom or an alkyl group. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. The alkyl group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear. The alkyl group may have a substituent. Examples of the substituent include the substituent T described above, and a hydroxy group is preferable. Preferably, at least one of R ¹¹ ~ R ¹³ is a hydrogen atom, more preferably all of R ¹¹ ~ R ¹³ is a hydrogen atom.

The metal azo pigment is a melamine compound (preferably represented by the formula (II) per mole of at least one anion selected from the azo compound represented by the formula (I) and the azo compound having a tautomer structure thereof. The compound is preferably contained in an amount of 0.05 to 4 mol, more preferably 0.5 to 2.5 mol, and still more preferably 1.0 to 2.0 mol.

In the metal azo pigment, it is preferable that at least one anion selected from an azo compound represented by the formula (I) and an azo compound having a tautomer structure thereof and a metal ion form a metal complex. For example, in the case of the divalent metal ion Me, a metal complex having a structure represented by the following formula (Ia) can be formed by the anion and the metal ion Me. Further, the metal ion Me may be bonded via a nitrogen atom in the tautomerization notation of the formula (Ia).

Preferred embodiments of the metal azo pigment used in the present invention include the metal azo pigments of the following embodiments (1) to (4), and the metal azo pigment of the embodiment (1) is preferable.

(1) At least one anion selected from the azo compound represented by the above formula (I) and an azo compound having a tautomer structure thereof, a metal ion containing at least Zn ²⁺ and Cu ²⁺ , and a melamine compound The metal azo pigment of the aspect containing these. In this embodiment, the total amount of Zn ²⁺ and Cu ²⁺ is preferably 95 to 100 mol%, more preferably 98 to 100 mol%, based on 1 mol of all metal ions of the metal azo pigment. The content is preferably 99.9 to 100 mol%, more preferably 100 mol%. The molar ratio of Zn ²⁺ to Cu ²⁺ in the metal azo pigment is preferably Zn ²⁺ : Cu ²⁺ = 199: 1 to 1:15, preferably 19: 1 to 1: 1. More preferably, it is 9: 1 to 2: 1. In this embodiment, the metal azo pigment may further contain a divalent or trivalent metal ion (hereinafter also referred to as metal ion Me1) other than Zn ²⁺ and Cu ²⁺ . As metal ions Me1, Ni ²⁺ , Al ³⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ²⁺ , Nd ³⁺ , Sm ²⁺ , Sm ³⁺ , Eu ²⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Yb ²⁺ , Yb ³⁺ , Er ³⁺ , Tm ³⁺ , Mg ^{2 +} , Ca ²⁺ , Sr ²⁺ , Mn ²⁺ , Y ³⁺ , Sc ³⁺ , Ti ²⁺ , Ti ³⁺ , Nb ³⁺ , Mo ²⁺ , Mo ³⁺ , V ²⁺ , V ³⁺ , Zr <^2+> , Zr ^<3+> , Cd <^2+> , Cr ^<3+> , Pb <^2+> , Ba ^<2+> are mentioned, Al ^<3+> , Fe ^<2+> , Fe ^<3+> , Co ^<2+> , Co ^<3+> , La ^<3+> , Ce ³⁺ , Pr ³⁺ , Nd ³⁺ , Sm ³⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Yb ³⁺ , Er ³⁺ , Tm ³⁺ , Mg ^2+, Ca ^2+, Sr ^2+, is preferably at least one selected from Mn ²⁺ and ^{^{^{Y 3+, Al 3+, Fe 2+}}} , Fe 3+, ^{^{^{o 2+, Co 3+, La 3+}}} , Ce 3+, Pr 3+, Nd 3+, Sm 3+, Tb 3+, further be at least one selected from Ho ³⁺ and Sr ²⁺ Particularly preferred is at least one selected from Al ³⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ and Co ³⁺ . The content of the metal ion Me1 is preferably 5 mol% or less, more preferably 2 mol% or less, and more preferably 0.1 mol% or less, based on 1 mol of all metal ions of the metal azo pigment. More preferably it is.

(2) It contains at least one anion selected from the azo compound represented by the above formula (I) and an azo compound having a tautomer structure thereof, a metal ion, and a melamine compound, and the metal ion is Ni ^{2 +} , Zn ²⁺ and at least one further metal ion Me2, the metal ion Me2 being La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ²⁺ , Nd ³⁺ , Sm ²⁺ , Sm ³⁺ , Eu ²⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Er ³⁺ , Tm ³⁺ , Yb ²⁺ , Yb ³⁺ , Mg ²⁺ , Ca ²⁺ , Sr ^{2 +} , Ba ²⁺ , Sc ³⁺ , Y ³⁺ , Ti ²⁺ , Ti ³⁺ , Zr ²⁺ , Zr ³⁺ , V ²⁺ , V ³⁺ , Nb ³⁺ , Cr ³⁺ , Mo ²⁺ , A metal azo pigment of an embodiment which is at least one selected from Mo ³⁺ , Mn ²⁺ , Cd ²⁺ , and Pb ²⁺ . Metal ions Me2 are La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ³⁺ , Sm ³⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Er ³⁺ , Tm It is preferably at least one selected from ³⁺ , Yb ³⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Y ³⁺ , and Mn ²⁺ , and La ³⁺ , Ce ³⁺ , Pr ³⁺ More preferably, it is at least one selected from Nd ³⁺ , Sm ³⁺ , Tb ³⁺ , Ho ³⁺ , and Sr ²⁺ . In this embodiment, Zn ²⁺ and Ni ²⁺ are contained in a total amount of 75 to 99.5 mol% based on 1 mol of all metal ions of the metal azo pigment, and 0.5 to 25 of the metal ion Me2 is contained. Preferably, it contains 78 to 95 mol% of Zn ²⁺ and Ni ²⁺ in total, and more preferably 5 to 22 mol% of metal ion Me2, and Zn ²⁺ and Ni ² More preferably, the total amount of ⁺ is 82 to 90 mol% and the metal ion Me2 is 10 to 18 mol%. The molar ratio of Zn ²⁺ to Ni ²⁺ in the metal azo pigment is preferably Zn ²⁺ : Ni ²⁺ = 90: 3 to 3:90, and is 80: 5 to 5:80. More preferred is 60:33 to 33:60.

(3) At least one anion selected from the azo compound represented by the above formula (I) and an azo compound having a tautomer structure thereof, a metal ion, and a melamine compound, wherein the metal ion is Ni ^{2 +} , Cu ²⁺ and at least one further metal ion Me3, the metal ion Me3 being La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ²⁺ , Nd ³⁺ , Sm ²⁺ , Sm ³⁺ , Eu ²⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Yb ²⁺ , Yb ³⁺ , Er ³⁺ , Tm ³⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Mn ²⁺ , Y ³⁺ , Sc ³⁺ , Ti ²⁺ , Ti ³⁺ , Nb ³⁺ , Mo ²⁺ , Mo ³⁺ , V ²⁺ , V ³⁺ , Zr ²⁺ , Zr ³⁺ , Cd The metal azo pigment of an embodiment which is at least one selected from ²⁺ , Cr ³⁺ , Pb ²⁺ and Ba ²⁺ . The metal ions Me3 are La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ³⁺ , Sm ³⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Yb ³⁺ , Er It is preferably at least one selected from ³⁺ , Tm ³⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Mn ²⁺ , and Y ³⁺ , and La ³⁺ , Ce ³⁺ , Pr ³⁺ More preferably, it is at least one selected from Nd ³⁺ , Sm ³⁺ , Tb ³⁺ , Ho ³⁺ , and Sr ²⁺ . In this embodiment, the total content of Cu ²⁺ and Ni ²⁺ is 70 to 99.5 mol%, based on 1 mol of the total metal ions of the metal azo pigment, and the metal ion Me3 is 0.5 to 30%. Preferably, it contains 75 to 95 mol% of Cu ²⁺ and Ni ²⁺ in total, and more preferably 5 to 25 mol% of metal ion Me3, and Cu ²⁺ and Ni ² More preferably, the total amount of ⁺ is 80 to 90 mol% and the metal ion Me3 is 10 to 20 mol%. The molar ratio of Cu ²⁺ to Ni ²⁺ in the metal azo pigment is preferably Cu ²⁺ : Ni ²⁺ = 42: 1 to 1:42, and is preferably 10: 1 to 1:10. It is more preferable that the ratio is 3: 1 to 1: 3.

(4) It contains at least one anion selected from the azo compound represented by the above formula (I) and an azo compound having a tautomer structure thereof, a metal ion, and a melamine compound, and the metal ion is Ni ^{2 +} And a metal ion Me4a, and the metal ion Me4a is La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ²⁺ , Nd ³⁺ , Sm ²⁺ , Sm ³⁺ , Eu ²⁺ , Eu ³⁺ , Gd ³ A metal azo pigment having an aspect of at least one selected from ⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Er ³⁺ , Tm ³⁺ , Yb ²⁺ and Yb ³⁺ . Metal ions Me4a are La ³⁺ , Ce ³⁺ , Pr ³⁺ , Nd ³⁺ , Sm ³⁺ , Eu ³⁺ , Gd ³⁺ , Tb ³⁺ , Dy ³⁺ , Ho ³⁺ , Er ³⁺ , Tm. preferably ³⁺ and is at least one selected from ^{^{^{Yb 3+, La 3+, Ce 3+}}} , Pr 3+, Nd 3+, Sm 3+, at least one selected from Tb ³⁺ and Ho ³⁺ More preferably it is a seed. In this embodiment, the total amount of Ni ²⁺ and metal ion Me4a is preferably 95 to 100 mol%, more preferably 98 to 100 mol%, based on 1 mol of all metal ions of the metal azo pigment. The content is preferably 99.9 to 100 mol%, more preferably 100 mol%. The molar ratio of Ni ²⁺ and metal ion Me4a in the metal azo pigment is preferably Ni ²⁺ : metal ion Me4a = 1: 1 to 19: 1, and preferably 2: 1 to 4: 1. More preferably, the ratio is 2.3: 1 to 3: 1. In this embodiment, the metal azo pigment may further contain a metal ion other than Ni ²⁺ and the metal ion Me4a (hereinafter also referred to as a metal ion Me4b). The metal ions Me4b include Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Ba ²⁺ , Sc ³⁺ , Y ³⁺ , Ti ²⁺ , Ti ³⁺ , Zr ²⁺ , Zr ³⁺ , V ²⁺ , V ³⁺ , Nb ³⁺ , Cr ³⁺ , Mo ²⁺ , Mo ³⁺ , Mn ²⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , Cu ²⁺ , Zn ²⁺ , Cd ^{2 +} , Al ³⁺ and Pb ²⁺ , Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Y ³⁺ , Mn ²⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , Cu It is preferably at least one selected from ²⁺ , Zn ²⁺ and Al ³⁺ , and Sr ²⁺ , Fe ²⁺ , Fe ³⁺ , Co ²⁺ , Co ³⁺ , Cu ²⁺ , Zn ²⁺ and More preferably, it is at least one selected from Al ³⁺ . The content of the metal ion Me4b is preferably 5 mol% or less, more preferably 2 mol% or less, more preferably 0.1 mol%, based on 1 mol of all metal ions of the metal azo pigment. More preferably, it is as follows.

The metal azo pigment includes a metal azo compound composed of at least one anion and a metal ion selected from the azo compound represented by the above formula (I) and an azo compound having a tautomer structure thereof, a melamine compound ( Preferably, an adduct is formed with the compound represented by the above formula (II). An adduct is understood to mean a molecular assembly. The bond between these molecules may be, for example, due to intermolecular interaction, may be due to Lewis acid-base interaction, or may be due to coordination bond or chain bond. Further, the adduct may have a structure such as an inclusion compound (clathrate) in which a guest molecule is incorporated in a lattice constituting a host molecule. Further, the adduct may have a structure such as a composite interlayer crystal (including an interstitial compound). A composite interlayer crystal is a chemical non-stoichiometric crystalline compound composed of at least two elements. Further, the adduct may be a mixed substitution crystal in which two substances form a joint crystal, and atoms of the second component are located at regular lattice positions of the first component.

The metal azo pigment may be a physical mixture or a chemical complex compound. Preferably, it is a physical mixture.

Regarding the above metal azo pigments, paragraph numbers 0011 to 0062 and 0137 to 0276 in JP-A-2017-171912, paragraph numbers 0010 to 0062 and 0138 to 0295 in JP-A-2017-171913, and JP-A-2017-171914. The descriptions of paragraph numbers 0011 to 0062 and 0139 to 0190 of the publication and paragraph numbers 0010 to 0065 and 0142 to 0222 of JP-A-2017-171915 can be referred to, and the contents thereof are incorporated in the present specification.

The content of other colorants is preferably 30% by mass or less based on the total solid content of the composition of the present invention. The lower limit is preferably 1% by mass or more, and more preferably 3% by mass or more.

The content of the yellow colorant is preferably 30% by mass or less based on the total solid content of the composition of the present invention. The lower limit is preferably 1% by mass or more, and more preferably 3% by mass or more.

The content of the purple colorant is preferably 30% by mass or less based on the total solid content of the composition of the present invention. The lower limit is preferably 1% by mass or more, and more preferably 3% by mass or more.

The total content of the yellow colorant and the purple colorant is preferably 30% by mass or less based on the total solid content of the composition of the present invention. The lower limit is preferably 1% by mass or more, and more preferably 3% by mass or more.

<< Solvent >>
The composition of the present invention contains a solvent. Examples of the solvent include organic solvents. The solvent is basically not particularly limited as long as the solubility of each component and the coating property of the composition are satisfied. Examples of the organic solvent include esters, ethers, ketones, aromatic hydrocarbons and the like. Regarding these details, paragraph number 0223 of International Publication No. WO2015 / 1666779 can be referred to, the contents of which are incorporated herein. Further, ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group can also be preferably used. Specific examples of the organic solvent include dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, Examples include cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate. In this invention, the organic solvent may be used individually by 1 type, and may be used in combination of 2 or more type. Also, 3-methoxy-N, N-dimethylpropanamide and 3-butoxy-N, N-dimethylpropanamide are preferable from the viewpoint of improving solubility. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent may be better reduced for environmental reasons. For example, it may be 50 mass ppm (parts per million) or less, 10 mass ppm or less, or 1 mass ppm or less with respect to the total amount of the organic solvent.

In the present invention, it is preferable to use a solvent having a low metal content, and the metal content of the solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, a solvent having a mass ppt (parts per trillation) level may be used, and such a high-purity solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).

Examples of the method for removing impurities such as metals from the solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. The filter pore diameter of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon.

The solvent may contain isomers (compounds having the same number of atoms but different structures). Moreover, only 1 type may be included and the isomer may be included multiple types.

In the present invention, the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.

The content of the solvent is preferably such that the solid content concentration (total solid content) of the composition is 5 to 50% by mass. The upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less. The lower limit is preferably 8% by mass or more, and preferably 10% by mass or more.

Moreover, it is preferable that the composition of the present invention does not substantially contain an environmentally regulated substance from the viewpoint of environmental regulations. In the present invention, substantially not containing an environmentally regulated substance means that the content of the environmentally regulated substance in the composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, It is more preferably 10 ppm by mass or less, and particularly preferably 1 ppm by mass or less. Examples of environmentally regulated substances include benzene; alkylbenzenes such as toluene and xylene; halogenated benzenes such as chlorobenzene, and the like. These are REACH (Registration Evaluation Authorization and Restriction of Chemicals) rules, PRTR (Pollutant Release and Transfer Register) Law, VOC (Volatile Organic Registered) and regulated as VOC (Volatile Organic Substances) The method is strictly regulated. These compounds may be used as a solvent when producing each component used in the composition of the present invention, and may be mixed into the composition as a residual solvent. It is preferable to reduce these substances as much as possible from the viewpoint of human safety and consideration for the environment. As a method for reducing the environmentally regulated substance, there is a method of heating and depressurizing the system so as to make it equal to or higher than the boiling point of the environmentally regulated substance to distill off the environmentally regulated substance from the system. In the case of distilling off a small amount of environmentally regulated substances, it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the corresponding solvent in order to increase efficiency. In addition, when a compound having radical polymerizability is contained, a polymerization inhibitor or the like may be added and distilled off under reduced pressure in order to suppress cross-linking between molecules due to progress of radical polymerization reaction during distillation under reduced pressure. Good. These distillation methods can be performed either at the raw material stage, the product obtained by reacting the raw material (for example, a resin solution after polymerization or a polyfunctional monomer solution), or a composition stage prepared by mixing these compounds. It is also possible in stages.

<< Curable compound >>
The composition of the present invention preferably contains a curable compound. As the curable compound, known compounds that can be cross-linked by radicals, acids, and heat can be used. Examples thereof include a compound having a group having an ethylenically unsaturated bond and a compound having a cyclic ether group. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. In the present invention, the curable compound is preferably a radical polymerizable compound or a cationic polymerizable compound, and more preferably a radical polymerizable compound.

The content of the curable compound is preferably 0.1 to 40% by mass with respect to the total solid content of the composition of the present invention. For example, the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. For example, the upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less. A curable compound may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types of sclerosing | hardenable compounds together, it is preferable that those total amounts become the said range.

(Radically polymerizable compound)
The radical polymerizable compound is not particularly limited as long as it is a compound that can be polymerized by the action of radicals. The radical polymerizable compound is preferably a compound having one or more groups having an ethylenically unsaturated bond, more preferably a compound having two or more groups having an ethylenically unsaturated bond, and a group having an ethylenically unsaturated bond. More preferred are compounds having 3 or more. The upper limit of the number of groups having an ethylenically unsaturated bond is, for example, preferably 15 or less, and more preferably 6 or less. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, and a (meth) acryloyl group is preferable. The radical polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, more preferably a 3 to 6 functional (meth) acrylate compound.

The radical polymerizable compound may be in the form of either a monomer or a polymer, but is preferably a monomer. The molecular weight of the monomer type radical polymerizable compound is preferably 200 to 3,000. The upper limit of the molecular weight is preferably 2500 or less, and more preferably 2000 or less. The lower limit of the molecular weight is preferably 250 or more, and more preferably 300 or more.

As radically polymerizable compounds, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; Nippon Kayaku Co., Ltd.) ), Dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, KAYARAD DPHA; Nippon Kayaku) NK ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and a structure in which these (meth) acryloyl groups are bonded via an ethylene glycol and / or propylene glycol residue Compounds (eg from Sartomer) Are sales, SR454, SR499), NK ester A-TMMT (manufactured by Shin-Nakamura Chemical Industry Co.), manufactured KAYARAD RP-1040, DPCA-20 (Nippon Kayaku Co.) and the like. Radical polymerizable compounds are trimethylolpropane tri (meth) acrylate, trimethylolpropane propyleneoxy modified tri (meth) acrylate, trimethylolpropane ethyleneoxy modified tri (meth) acrylate, isocyanuric acid ethyleneoxy modified tri (meth). It is also preferable to use a trifunctional (meth) acrylate compound such as acrylate or pentaerythritol tri (meth) acrylate. Commercially available products of trifunctional (meth) acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305. , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) And TMPEOTA (manufactured by Daicel Ornex Co., Ltd.).

As the radical polymerizable compound, a compound having an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group can be used. Examples of commercially available radical polymerizable compounds having an acid group include Aronix M-305, M-510, and M-520 (manufactured by Toagosei Co., Ltd.). The acid value of the radically polymerizable compound having an acid group is preferably from 0.1 to 40 mgKOH / g. The lower limit is preferably 5 mgKOH / g or more. The upper limit is preferably 30 mgKOH / g or less.

The radical polymerizable compound is also preferably a compound having a caprolactone structure. The radical polymerizable compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentylol. Mention may be made of ε-caprolactone-modified polyfunctional (meth) acrylates obtained by esterifying polyhydric alcohols such as pentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone. it can. Regarding the radically polymerizable compound having a caprolactone structure, the description in paragraph numbers 0042 to 0045 of JP2013-253224A can be referred to, and the contents thereof are incorporated in the present specification. Examples of the compound having a caprolactone structure include DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series.

As the radically polymerizable compound, a compound having a group having an ethylenically unsaturated bond and an alkyleneoxy group can also be used. The compound having an ethylenically unsaturated bond and an alkyleneoxy group is preferably a compound having an ethylenically unsaturated bond and an ethyleneoxy group and / or a propyleneoxy group, and has an ethylenically unsaturated bond. A compound having a group and an ethyleneoxy group is more preferable, and a tri- to hexafunctional (meth) acrylate compound having 4 to 20 ethyleneoxy groups is more preferable. Examples of commercially available compounds having an ethylenically unsaturated bond and an alkyleneoxy group include SR-494, a tetrafunctional (meth) acrylate having 4 ethyleneoxy groups manufactured by Sartomer, and 3 isobutyleneoxy groups. Examples thereof include KAYARAD TPA-330, which is a trifunctional (meth) acrylate.

Radical polymerizable compounds include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, Also suitable are urethane compounds having an ethylene oxide skeleton as described in Japanese Patent Publication Nos. 58-49860, 56-17654, 62-39417, and 62-39418. Further, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. Can do. Commercially available products include UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T- 600, manufactured by AI-600 (Kyoeisha Chemical Co., Ltd.) and the like.
Radical polymerizable compounds include compounds described in JP 2017-48367 A, JP 6057891 A, JP 6031807 A, compounds described in JP 2017-194462 A, 8 UH- It is also preferable to use 1006, 8UH-1012 (above, manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), or the like.

When the composition of the present invention contains a radical polymerizable compound, the content of the radical polymerizable compound is preferably 0.1 to 40% by mass with respect to the total solid content of the composition of the present invention. For example, the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. For example, the upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less. A radically polymerizable compound may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types of radically polymerizable compounds together, it is preferable that those total amount becomes the said range.

(Cationically polymerizable compound)
Examples of the cationic polymerizable compound include compounds having a cationic polymerizable group. Examples of the cationic polymerizable group include cyclic ether groups such as epoxy groups and oxetanyl groups, and unsaturated carbon double bond groups such as vinyl ether groups and isobutene groups. The cationically polymerizable compound is preferably a compound having a cyclic ether group, and more preferably a compound having an epoxy group.

Examples of the compound having an epoxy group include a compound having one or more epoxy groups in one molecule, and a compound having two or more epoxy groups is preferable. It is preferable to have 1 to 100 epoxy groups in one molecule. The upper limit of the epoxy group can be, for example, 10 or less, or 5 or less. The lower limit of the epoxy group is preferably 2 or more.

The compound having an epoxy group may be a low molecular weight compound (for example, a molecular weight of less than 2000, or even a molecular weight of less than 1000), or a macromolecule (for example, a molecular weight of 1000 or more, in the case of a polymer, the weight average molecular weight is 1000 or more). The weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5000 or less, and still more preferably 3000 or less.

When the compound having an epoxy group is a low molecular compound, for example, a compound represented by the following formula (EP1) can be mentioned.

In the formula (EP1), R ^EP1 to R ^EP3 each represent a hydrogen atom, a halogen atom, or an alkyl group, and the alkyl group may have a cyclic structure, and may have a substituent. Also good. R ^EP1 and R ^EP2 and R ^EP2 and R ^EP3 may be bonded to each other to form a ring structure. ^QEP represents a single bond or an ^nEP- valent organic group. R ^EP1 ~ R ^EP3 combines with Q ^EP may form a ring structure. ^nEP represents an integer of 2 or more, preferably 2 to 10, and more preferably 2 to 6. However, n ^EP is 2 when Q ^EP is a single bond.
Details of R ^EP1 to R ^EP3 and Q ^EP can be referred to the descriptions in paragraph numbers 0087 to 0088 of Japanese Patent Application Laid-Open No. 2014-089408, the contents of which are incorporated herein. Specific examples of the compound represented by the formula (EP1) include a compound described in paragraph 0090 of JP2014-089408A and a compound described in paragraph number 0151 of JP2010-054632A. The contents are incorporated herein.

Examples of commercially available low molecular weight compounds include ADEKA GLYCIROL series (for example, ADEKA GLYCIROL ED-505) manufactured by ADEKA Co., Ltd., and Epolide series (for example, EPOLID GT401, etc.) manufactured by Daicel Corporation. It is done.

An epoxy resin can be preferably used for the compound having an epoxy group. Examples of the epoxy resin include an epoxy resin that is a glycidyl etherified product of a phenol compound, an epoxy resin that is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, and a glycidyl ester type. Epoxy resins, glycidylamine epoxy resins, epoxy resins obtained by glycidylation of halogenated phenols, condensates of silicon compounds having an epoxy group with other silicon compounds, polymerizable unsaturated compounds having an epoxy group and others Examples thereof include copolymers with other polymerizable unsaturated compounds. The epoxy equivalent of the epoxy resin is preferably 310 to 3300 g / eq, more preferably 310 to 1700 g / eq, and still more preferably 310 to 1000 g / eq.

Examples of commercially available epoxy resins include EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G -1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (above, manufactured by NOF Corporation, epoxy group-containing polymer) and the like.

In the present invention, the compound having an epoxy group includes paragraph numbers 0034 to 0036 of JP2013-011869A, paragraphs 0147 to 0156 of JP2014043556A, paragraph number 0085 of JP2014089408A. To 0092 and JP-A No. 2017-179172 can also be used. These contents are incorporated herein.

When the composition of the present invention contains a cationic polymerizable compound, the content of the cationic polymerizable compound is preferably 0.1 to 40% by mass with respect to the total solid content of the composition of the present invention. For example, the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. For example, the upper limit is more preferably 30% by mass or less, and still more preferably 20% by mass or less. A cationically polymerizable compound may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types of cationically polymerizable compounds together, it is preferable that those total amounts become the said range.
In the case where the composition of the present invention contains a radical polymerizable compound and a cationic polymerizable compound, the mass ratio of the two is preferably radical polymerizable compound: cation polymerizable compound = 100: 1 to 100: 400, 1 to 100: 100 is more preferable.

<< photopolymerization initiator >>
The composition of the present invention can contain a photopolymerization initiator. Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator. It is preferable to select and use according to the kind of curable compound. When a radical polymerizable compound is used as the curable compound, it is preferable to use a photo radical polymerization initiator as the photo polymerization initiator. When a cationic polymerizable compound is used as the curable compound, it is preferable to use a cationic photopolymerization initiator as the photopolymerization initiator. There is no restriction | limiting in particular as a photoinitiator, It can select suitably from well-known photoinitiators. For example, a compound having photosensitivity to light in the ultraviolet region to the visible region is preferable.

The content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and still more preferably 1 to 20% by mass with respect to the total solid content of the composition of the present invention. If the content of the photopolymerization initiator is within the above range, better sensitivity and pattern formability can be obtained. The composition of this invention may contain only 1 type of photoinitiators, and may contain 2 or more types. When two or more photopolymerization initiators are included, the total amount thereof is preferably within the above range.

(Photo radical polymerization initiator)
Examples of the photo radical polymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides. Thio compounds, ketone compounds, aromatic onium salts, α-hydroxy ketone compounds, α-amino ketone compounds, and the like. Photopolymerization initiators are trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazoles from the viewpoint of exposure sensitivity. Dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound, cyclopentadiene-benzene-iron complex, halomethyloxadiazole compound and 3-aryl-substituted coumarin compound are preferred, oxime compound, α-hydroxyketone compound, α- A compound selected from an aminoketone compound and an acylphosphine compound is more preferable, and an oxime compound is still more preferable. As the radical photopolymerization initiator, the description in paragraphs 0065 to 0111 of JP-A-2014-130173 can be referred to, and the contents thereof are incorporated herein.

Examples of commercially available α-hydroxyketone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (above, manufactured by BASF). Examples of commercially available α-aminoketone compounds include IRGACURE-907, IRGACURE-369, IRGACURE-379, IRGACURE-379EG (manufactured by BASF). Examples of commercially available acylphosphine compounds include IRGACURE-819 and DAROCUR-TPO (above, manufactured by BASF).

Examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, compounds described in JP-A No. 2006-342166, J.P. C. S. Perkin II (1979, pp.1653-1660), J.M. C. S. Compounds described in Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), compounds described in Japanese Patent Application Laid-Open No. 2000-66385, Compounds described in JP-A No. 2000-80068, compounds described in JP-T No. 2004-534797, compounds described in JP-A No. 2006-342166, compounds described in JP-A No. 2017-19766, patent No. Examples thereof include compounds described in Japanese Patent No. 6065596, compounds described in International Publication WO2015 / 152153, compounds described in International Publication WO2017 / 051680, and the like. Specific examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxy And imino-1-phenylpropan-1-one. Commercially available products include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (above, manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adekaoptomer N-1919 (Photopolymerization initiator 2 manufactured by ADEKA Corporation, described in JP 2012-14052 A) can also be used. As the oxime compound, a compound having no coloring property or a compound having high transparency and hardly discolored is used. It is also preferable. Examples of commercially available products include Adeka Arcles NCI-730, NCI-831, and NCI-930 (above, manufactured by ADEKA Corporation).

In the present invention, an oxime compound having a fluorene ring can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466. This content is incorporated herein.

In the present invention, an oxime compound having a fluorine atom can also be used as a radical photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and JP-A 2013-164471. Compound (C-3). This content is incorporated herein.

In the present invention, an oxime compound having a nitro group can be used as a radical photopolymerization initiator. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of JP2013-114249A, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466A, Examples include compounds described in paragraph Nos. 0007 to 0025 of Japanese Patent No. 4230711, Adeka Arcles NCI-831 (manufactured by ADEKA Corporation).

In the present invention, an oxime compound having a benzofuran skeleton can also be used as a radical photopolymerization initiator. Specific examples include OE-01 to OE-75 described in International Publication No. WO2015 / 036910.

Specific examples of oxime compounds that are preferably used in the present invention are shown below, but the present invention is not limited thereto.

The oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, and more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm. The molar extinction coefficient of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high from the viewpoint of sensitivity, more preferably 1,000 to 300,000, and preferably 2,000 to 300,000. Is more preferably 5,000 to 200,000. The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) at a concentration of 0.01 g / L using an ethyl acetate solvent.

In the present invention, a bifunctional or trifunctional or higher functional photo radical polymerization initiator may be used as the photo radical polymerization initiator. By using such a radical photopolymerization initiator, two or more radicals are generated from one molecule of the radical photopolymerization initiator, so that good sensitivity can be obtained. In addition, when a compound having an asymmetric structure is used, the crystallinity is lowered and the solubility in a solvent or the like is improved, the precipitation with time is less likely to occur, and the temporal stability of the composition can be improved. Specific examples of the bifunctional or trifunctional or higher functional photopolymerization initiators are disclosed in JP 2010-527339 A, JP 2011-524436 A, International Publication WO 2015/004565, and JP 2016-532675 A. Dimers of oxime compounds described in Paragraph Nos. 0417 to 0412 and Paragraph Nos. 0039 to 0055 of International Publication WO2017 / 033680, Compound (E) and Compound described in JP 2013-522445 A G), Cmpds 1 to 7 described in International Publication WO2016 / 034963, Oxime Esters Photoinitiators described in Paragraph No. 0007 of JP-T-2017-523465, JP-A-2017-167399 Listed in paragraph numbers 0020-0033 Initiator, a photopolymerization initiator and (A) are exemplified as described in paragraph Nos. 0017 to 0026 of JP-A-2017-151342.

It is also preferable to use an oxime compound and an α-aminoketone compound as the photoradical polymerization initiator. By using both in combination, the developability is improved and a pattern having excellent rectangularity can be easily formed. When the oxime compound and the α-aminoketone compound are used in combination, the α-aminoketone compound is preferably 50 to 600 parts by mass, more preferably 150 to 400 parts by mass with respect to 100 parts by mass of the oxime compound.

The content of the photo radical polymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and still more preferably 1 to 20% by mass with respect to the total solid content of the composition of the present invention. . If the content of the radical photopolymerization initiator is within the above range, better sensitivity and pattern formability can be obtained. The composition of this invention may contain only 1 type of radical photopolymerization initiators, and may contain 2 or more types. When two or more kinds of radical photopolymerization initiators are included, the total amount thereof is preferably within the above range.

(Photocationic polymerization initiator)
A photoacid generator is mentioned as a photocationic polymerization initiator. Photoacid generators include onium salt compounds such as diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazodisulfones, disulfones, o-nitrobenzyls that generate acids upon decomposition by light irradiation. Examples thereof include sulfonate compounds such as sulfonate. Details of the photocationic polymerization initiator can be referred to the descriptions in paragraphs 0139 to 0214 of JP-A-2009-258603, the contents of which are incorporated herein.

The content of the cationic photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and still more preferably 1 to 20% by mass with respect to the total solid content of the composition of the present invention. . When the content of the cationic photopolymerization initiator is within the above range, better sensitivity and pattern forming property can be obtained. The composition of this invention may contain only 1 type of photocationic polymerization initiators, and may contain 2 or more types. When 2 or more types of photocationic polymerization initiators are contained, it is preferable that those total amount becomes the said range.

<< Polyfunctional thiol >>
The composition of the present invention may contain a polyfunctional thiol. A polyfunctional thiol is a compound having two or more thiol (SH) groups. By using the polyfunctional thiol together with the above-mentioned photo radical polymerization initiator, it acts as a chain transfer agent in the radical polymerization process after light irradiation, and a thiyl radical is generated that is less susceptible to polymerization inhibition by oxygen. Can be increased. In particular, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable.

Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropioate. , Trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3- Mercaptopropionate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-mercaptopropioate) Dipentaerythritol hexakis (3-mercaptopropionate), trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s -Triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine and the like. Moreover, the compound of the following structure is also mentioned.

The content of the polyfunctional thiol is preferably 0.1 to 20% by mass, more preferably 0.1 to 15% by mass, and still more preferably 0.1 to 10% by mass with respect to the total solid content of the composition of the present invention. . The composition of the present invention may contain only one kind of polyfunctional thiol, or may contain two or more kinds. When 2 or more types are included, the total amount thereof is preferably within the above range.

<< Resin >>
The composition of the present invention preferably contains a resin. The resin is blended, for example, for the purpose of dispersing a pigment or the like in the composition or the purpose of a binder. A resin used mainly for dispersing pigments is also called a dispersant. However, such use of the resin is an example, and the resin can be used for purposes other than such use.

The weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 3,000 or more, and more preferably 5,000 or more.

As the resin, (meth) acrylic resin, epoxy resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, Examples thereof include polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, and styrene resin. One of these resins may be used alone, or two or more thereof may be mixed and used. In addition, the resin includes a resin described in Examples of International Publication WO2016 / 088845, a resin described in JP2017-57265A, a resin described in JP2017-32685A, and JP2017. The resin described in JP-0775248, the resin described in JP2017-0666240, or the resin described in JP2017-167513 can also be used, the contents of which are incorporated herein. It is. A resin having a fluorene skeleton can also be preferably used. Examples of the resin having a fluorene skeleton include resins having the following structure. In the following structural formula, A is the residue of carboxylic dianhydride selected from pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride and diphenyl ether tetracarboxylic dianhydride. And M is a phenyl group or a benzyl group. Regarding the resin having a fluorene skeleton, the description of US Patent Application Publication No. 2017/0102610 can be referred to, and the contents thereof are incorporated herein.

The resin used in the present invention may have an acid group. Examples of the acid group include a carboxyl group, a phosphate group, a sulfo group, and a phenolic hydroxy group, and a carboxyl group is preferable. These acid groups may be used alone or in combination of two or more. Resins having acid groups can also be used as alkali-soluble resins.

As the resin having an acid group, a polymer having a carboxyl group in the side chain is preferable. Specific examples include methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and alkali-soluble resins such as novolac resins. Examples thereof include phenol resins, acidic cellulose derivatives having a carboxyl group in the side chain, and resins obtained by adding an acid anhydride to a polymer having a hydroxy group. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Examples of vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene Macromonomer, polymethylmethacrylate macromonomer, and the like. As other monomers, N-substituted maleimide monomers described in JP-A-10-300922 such as N-phenylmaleimide and N-cyclohexylmaleimide can also be used. In addition, only 1 type may be sufficient as the other monomer copolymerizable with these (meth) acrylic acids, and 2 or more types may be sufficient as it.

The resin having an acid group may further have a polymerizable group. Examples of the polymerizable group include an allyl group, a methallyl group, and a (meth) acryloyl group. Commercially available products include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (carboxyl group-containing polyurethane acrylate oligomer, Diamond Shamrock Co., Ltd.), Biscote R-264, KS resist 106 (all of which are Osaka organic Chemical Industry Co., Ltd.), Cyclomer series (for example, ACA230AA, ACA250, etc.), Plaxel CF200 series (both manufactured by Daicel Corporation), Ebecryl 3800 (manufactured by Daicel UCB Corporation), Acrylure RD-F8 (( (Manufactured by Nippon Shokubai Co., Ltd.).

Resins having an acid group include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) Multi-component copolymers composed of acrylate / (meth) acrylic acid / other monomers can be preferably used. Further, a copolymer of 2-hydroxyethyl (meth) acrylate, a 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer described in JP-A-7-140654, 2 -Hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene A macromonomer / benzyl methacrylate / methacrylic acid copolymer can also be preferably used.

The resin having an acid group is a monomer containing a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”). A polymer containing a repeating unit derived from a component is also preferred.

In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

In the formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the formula (ED2), the description in JP 2010-168539 A can be referred to.

As a specific example of the ether dimer, for example, paragraph number 0317 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification. Only one type of ether dimer may be used, or two or more types may be used.

The resin having an acid group may contain a repeating unit derived from a compound represented by the following formula (X).

In formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or a benzene ring that may contain a benzene ring. Represents an alkyl group. n represents an integer of 1 to 15.

Regarding the resin having an acid group, description in paragraph Nos. 0558 to 0571 of JP2012-208494A (paragraph No. 0685 to 0700 in the corresponding US Patent Application Publication No. 2012/0235099), JP2012-198408 The description of paragraph numbers 0076 to 0099 of the publication can be referred to, and the contents thereof are incorporated in the present specification. Moreover, the resin which has an acid group can also use a commercial item. For example, acrylic base FF-426 (manufactured by Fujikura Kasei Co., Ltd.) can be used.

The acid value of the resin having an acid group is preferably 30 to 200 mgKOH / g. The lower limit is preferably 50 mgKOH / g or more, and more preferably 70 mgKOH / g or more. The upper limit is preferably 150 mgKOH / g or less, and more preferably 120 mgKOH / g or less.

Examples of the resin having an acid group include resins having the following structure. In the following structural formulas, Me represents a methyl group.

The composition of the present invention can also contain a resin as a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin). Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups. The acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups occupies 70 mol% or more when the total amount of acid groups and basic groups is 100 mol%. A resin consisting only of groups is more preferred. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and still more preferably 60 to 105 mgKOH / g. The basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger than the amount of acid groups. The basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of acid groups and basic groups is 100 mol%. The basic group possessed by the basic dispersant is preferably an amino group.

The resin used as the dispersant preferably contains a repeating unit having an acid group. When the resin used as the dispersant contains a repeating unit having an acid group, a residue generated on the base of the pixel can be further reduced when a pattern is formed by a photolithography method.

The resin used as the dispersant is also preferably a graft copolymer. Since the graft copolymer has an affinity for the solvent by the graft chain, it is excellent in pigment dispersibility and dispersion stability after aging. Details of the graft copolymer can be referred to the descriptions in paragraphs 0025 to 0094 of JP2012-255128A, the contents of which are incorporated herein. Specific examples of the graft copolymer include the following resins. The following resins are also resins having acid groups (alkali-soluble resins). Examples of the graft copolymer include resins described in JP-A-2012-255128, paragraphs 0072 to 0094, the contents of which are incorporated herein.

In the present invention, as the resin (dispersant), it is also preferable to use an oligoimine dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The oligoimine-based dispersant has a structural unit having a partial structure X having a functional group of pKa14 or less, a side chain containing a side chain Y having 40 to 10,000 atoms, and a main chain and a side chain. A resin having at least one basic nitrogen atom is preferred. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom. Regarding the oligoimine-based dispersant, the description of paragraph numbers 0102 to 0166 in JP 2012-255128 A can be referred to, and the contents thereof are incorporated herein. As the oligoimine-based dispersant, resins having the following structures and resins described in paragraph numbers 0168 to 0174 of JP 2012-255128 A can be used.

The dispersant is also available as a commercial product, and specific examples thereof include BYK2000 (manufactured by Big Chemie Japan Co., Ltd.). In addition, pigment dispersants described in paragraph numbers 0041 to 0130 of JP-A-2014-130338 can also be used, the contents of which are incorporated herein. Moreover, the resin etc. which have the acid group mentioned above can also be used as a dispersing agent.

When the composition of the present invention contains a resin, the resin content is preferably 1 to 50% by mass with respect to the total solid content of the composition of the present invention. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, and particularly preferably 10% by mass or more. The upper limit is more preferably 40% by mass or less, and still more preferably 30% by mass or less. The content of the resin having an acid group is preferably 1 to 50% by mass with respect to the total solid content of the composition of the present invention. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, and particularly preferably 10% by mass or more. The upper limit is more preferably 40% by mass or less, and still more preferably 30% by mass or less. The composition of the present invention may contain only one kind of resin, or may contain two or more kinds of resins. When 2 or more types are included, the total amount thereof is preferably within the above range.

When the composition of the present invention contains a radical polymerizable compound and a resin, the mass ratio of the radical polymerizable compound and the resin is preferably radical polymerizable compound / resin = 0.4 to 1.4. The lower limit of the mass ratio is preferably 0.5 or more, and more preferably 0.6 or more. The upper limit of the mass ratio is preferably 1.3 or less, and more preferably 1.2 or less. If the said mass ratio is the said range, the pattern which was more excellent in the rectangularity can be formed.
The mass ratio between the radical polymerizable compound and the resin having an acid group is preferably radical polymerizable compound / resin having an acid group = 0.4 to 1.4. The lower limit of the mass ratio is preferably 0.5 or more, and more preferably 0.6 or more. The upper limit of the mass ratio is preferably 1.3 or less, and more preferably 1.2 or less. If the said mass ratio is the said range, the pattern which was more excellent in the rectangularity can be formed.

<< Pigment derivative >>
The composition of the present invention may further contain a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of the pigment is substituted with an acid group, a basic group, a group having a salt structure, or a phthalimidomethyl group. As the pigment derivative, a compound represented by the formula (B1) is preferable.

In formula (B1), P represents a dye structure, L represents a single bond or a linking group, X represents an acid group, a basic group, a group having a salt structure, or a phthalimidomethyl group, and m is an integer of 1 or more. N represents an integer of 1 or more. When m is 2 or more, a plurality of L and X may be different from each other, and when n is 2 or more, a plurality of X may be different from each other.

As the dye structure represented by P, pyrrolopyrrole dye structure, diketopyrrolopyrrole dye structure, quinacridone dye structure, anthraquinone dye structure, dianthraquinone dye structure, benzoisoindole dye structure, thiazine indigo dye structure, azo dye structure, quinophthalone At least one selected from a dye structure, a phthalocyanine dye structure, a naphthalocyanine dye structure, a dioxazine dye structure, a perylene dye structure, a perinone dye structure, a benzimidazolone dye structure, a benzothiazole dye structure, a benzimidazole dye structure, and a benzoxazole dye structure More preferably, at least one selected from a pyrrolopyrrole dye structure, a diketopyrrolopyrrole dye structure, a quinacridone dye structure and a benzimidazolone dye structure is more preferable, and pyrrolopyrrole Containing structure is particularly preferred.

Examples of the linking group represented by L include a hydrocarbon group, a heterocyclic group, —NR—, —SO ₂ —, —S—, —O—, —CO—, or a combination thereof. R represents a hydrogen atom, an alkyl group or an aryl group.

Examples of the acid group represented by X include a carboxyl group, a sulfo group, a carboxylic acid amide group, a sulfonic acid amide group, and an imido acid group. As the carboxylic acid amide group, a group represented by —NHCOR ^X1 is preferable. As the sulfonic acid amide group, a group represented by —NHSO ₂ R ^X2 is preferable. As the imido acid group, a group represented by —SO ₂ NHSO ₂ R ^X3 , —CONHSO ₂ R ^X4 , —CONHCOR ^X5 or —SO ₂ NHCOR ^X6 is preferable. R ^X1 to R ^X6 each independently represent a hydrocarbon group or a heterocyclic group. The hydrocarbon group and heterocyclic group represented by R ^X1 to R ^X6 may further have a substituent. Examples of the substituent include the substituent T described above, preferably a halogen atom, and more preferably a fluorine atom. Examples of the basic group represented by X include an amino group. The amino group is preferably a group represented by —NR ¹⁰⁰ R ¹⁰¹ . R ¹⁰⁰ and R ¹⁰¹ each independently represents a hydrogen atom, a hydrocarbon group or a heterocyclic group. The hydrocarbon group and heterocyclic group represented by R ¹⁰⁰ and R ¹⁰¹ may have a substituent. Examples of the substituent include the substituent T described above. The phthalimidomethyl group represented by X may be unsubstituted or may have a substituent. Examples of the substituent include the substituent T described above. Examples of the salt structure represented by X include the salts of the acid groups or basic groups described above.

Examples of the pigment derivative include compounds having the following structure. Also, JP-A-56-118462, JP-A-63-264673, JP-A-1-217077, JP-A-3-9961, JP-A-3-26767, JP-A-3-153780. JP-A-3-45662, JP-A-4-285669, JP-A-6-145546, JP-A-6-212088, JP-A-6-240158, JP-A-10-30063, Described in JP-A-10-195326, paragraph numbers 0086 to 0098 of international publication WO2011 / 024896, paragraph numbers 0063 to 0094 of international publication WO2012 / 102399, paragraph number 0082 of international publication WO2017 / 038252, etc. The compounds described in Japanese Patent No. 5299151 can also be used. , The contents of which are incorporated herein.

When the composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the pigment. The lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more. The upper limit is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less. If content of a pigment derivative is the said range, the dispersibility of a pigment can be improved and aggregation of a pigment can be suppressed efficiently. Only one pigment derivative may be used, or two or more pigment derivatives may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

<< Polymerization inhibitor >>
The composition of the present invention can contain a polymerization inhibitor. Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), Examples include 2,2′-methylenebis (4-methyl-6-tert-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salt, primary cerium salt, etc.). Of these, p-methoxyphenol is preferred. The content of the polymerization inhibitor is preferably 0.0001 to 5% by mass with respect to the composition of the present invention.

<< Silane coupling agent >>
The composition of the present invention can contain a silane coupling agent. In the present invention, the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups. The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. As a hydrolysable group, a halogen atom, an alkoxy group, an acyloxy group etc. are mentioned, for example, An alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than hydrolyzable groups include vinyl groups, (meth) acryloyl groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, isocyanate groups, and phenyl groups. (Meth) acryloyl groups and epoxy groups are preferred. Examples of the silane coupling agent include compounds described in paragraph Nos. 0018 to 0036 of JP-A-2009-288703, and compounds described in paragraph numbers 0056 to 0066 of JP-A-2009-242604. Incorporated in the description.

The content of the silane coupling agent is preferably 0.01 to 15.0 mass%, more preferably 0.05 to 10.0 mass%, based on the total solid content of the composition of the present invention. The silane coupling agent may be only one type or two or more types. In the case of two or more types, the total amount is preferably within the above range.

<< Surfactant >>
The composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. As for the surfactant, paragraph numbers 0238 to 0245 of International Publication No. WO2015 / 166679 can be referred to, the contents of which are incorporated herein.

In the present invention, the surfactant is preferably a fluorosurfactant. By including a fluorosurfactant in the composition of the present invention, liquid properties (particularly fluidity) can be further improved, and liquid-saving properties can be further improved. In addition, a film with small thickness unevenness can be formed.

The fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the composition.

Examples of the fluorosurfactant include surfactants described in paragraph Nos. 0060 to 0064 of JP-A No. 2014-41318 (paragraph Nos. 0060 to 0064 of International Publication No. 2014/17669), JP-A No. 2011-2011, and the like. Examples include surfactants described in paragraph Nos. 0117 to 0132 of No. 132503, the contents of which are incorporated herein. Examples of commercially available fluorosurfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS. -330 (above, manufactured by DIC Corporation), Florard FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA) .

In addition, the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which the fluorine atom is volatilized by cleavage of the functional group containing the fluorine atom when heated is suitably used. Can be used. Examples of such a fluorosurfactant include Megafac DS series manufactured by DIC Corporation (Chemical Industry Daily, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016). -21.

Further, as the fluorosurfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. Such a fluorine-based surfactant can be referred to the description in JP-A-2016-216602, the contents of which are incorporated herein.

As the fluorosurfactant, a block polymer can be used. Examples thereof include compounds described in JP2011-89090A. The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. The following compounds are also exemplified as the fluorosurfactant used in the present invention.

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000. In the above compounds,% indicating the ratio of repeating units is mol%.

Further, as the fluorosurfactant, a fluoropolymer having an ethylenically unsaturated group in the side chain can also be used. Specific examples thereof include compounds described in paragraph Nos. 0050 to 0090 and paragraph Nos. 0289 to 0295 of JP2010-164965A, for example, Megafac RS-101, RS-102, RS-718K manufactured by DIC Corporation. RS-72-K and the like. As the fluorine-based surfactant, compounds described in paragraph numbers 0015 to 0158 of JP-A No. 2015-117327 can also be used.

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF ), Tetronic 304, 701, 704, 901, 904, 150R1 (BAS) Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Pionein D-6112, D-6112-W, D -6315 (manufactured by Takemoto Yushi Co., Ltd.), Olphine E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) and the like.

The content of the surfactant is preferably 0.001% by mass to 5.0% by mass and more preferably 0.005% by mass to 3.0% by mass with respect to the total solid content of the composition of the present invention. Only one type of surfactant may be used, or two or more types may be used. When using 2 or more types of surfactant, it is preferable that those total amount becomes said range.

<< UV absorber >>
The composition of the present invention can contain an ultraviolet absorber. As the ultraviolet absorber, a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound, or the like can be used. Details of these are described in paragraph numbers 0052 to 0072 of JP2012-208374A, paragraph numbers 0317 to 0334 of JP2013-68814A, and paragraph numbers 0061 to 0080 of JP2016-162946A. Which are incorporated herein by reference. Specific examples of the ultraviolet absorber include compounds having the following structure. Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by Daito Chemical Co., Ltd.). Moreover, as a benzotriazole compound, the MYUA series (Chemical Industry Daily, February 1, 2016) made from Miyoshi oil and fat is mentioned.

The content of the ultraviolet absorber is preferably from 0.01 to 10% by mass, more preferably from 0.01 to 5% by mass, based on the total solid content of the composition of the present invention. Only one type of ultraviolet absorber may be used, or two or more types may be used. When using 2 or more types of ultraviolet absorbers, it is preferable that those total amount becomes the said range.

<< Antioxidant >>
The composition of the present invention can contain an antioxidant. Examples of the antioxidant include a phenol compound, a phosphite compound, and a thioether compound. As the phenol compound, any phenol compound known as a phenol-based antioxidant can be used. Preferable phenolic compounds include hindered phenolic compounds. A compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxyl group is preferred. The aforementioned substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. The antioxidant is also preferably a compound having a phenol group and a phosphite group in the same molecule. Moreover, phosphorus antioxidant can also be used suitably for antioxidant. As the phosphorus-based antioxidant, tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphine-6 -Yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-2-yl ) Oxy] ethyl] amine, ethylbisphosphite (2,4-di-tert-butyl-6-methylphenyl), and the like. Commercially available antioxidants include, for example, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G and ADK STAB AO-80. Adeka Stub AO-330 (above, ADEKA Co., Ltd.) and the like. Moreover, the polyfunctional hindered amine antioxidant described in international publication WO17 / 006600 and the antioxidant described in international publication WO2017 / 164024 can also be used as antioxidant.

The content of the antioxidant is preferably 0.01 to 20% by mass, and more preferably 0.3 to 15% by mass, based on the total solid content of the composition of the present invention. Only one type of antioxidant may be used, or two or more types may be used. When using 2 or more types of antioxidant, it is preferable that those total amount becomes the said range.

<< Other ingredients >>
The composition of the present invention may contain a sensitizer, a curing accelerator, a filler, a thermosetting accelerator, a plasticizer, and other auxiliary agents (for example, conductive particles, a filler, an antifoaming agent, a difficult agent, if necessary). A flame retardant, a leveling agent, a peeling accelerator, a fragrance, a surface tension adjusting agent, a chain transfer agent, and the like). Properties such as film properties can be adjusted by appropriately containing these components. These components are described, for example, in paragraphs No. 0183 and later of JP2012-003225A (corresponding to paragraph No. 0237 of US Patent Application Publication No. 2013/0034812) and paragraphs of JP2008-250074A. The description of numbers 0101 to 0104, 0107 to 0109, and the like can be referred to, and the contents thereof are incorporated in this specification. Moreover, the composition of this invention may contain a latent antioxidant as needed. The latent antioxidant is a compound in which a site functioning as an antioxidant is protected with a protecting group, and is heated at 100 to 250 ° C. or heated at 80 to 200 ° C. in the presence of an acid / base catalyst. As a result, a compound that functions as an antioxidant due to elimination of the protecting group can be mentioned. Examples of the latent antioxidant include compounds described in International Publication WO2014 / 021023, International Publication WO2017 / 030005, and Japanese Unexamined Patent Publication No. 2017-008219. Examples of commercially available products include Adeka Arcles GPA-5001 (manufactured by ADEKA Corporation).

The solid content concentration of the composition of the present invention is preferably 5 to 50% by mass. The upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less. The lower limit is preferably 8% by mass or more, and more preferably 10% by mass or more.

The viscosity (23 ° C.) of the composition of the present invention is preferably 1 to 100 mPa · s, for example, when a film is formed by coating. The lower limit is more preferably 2 mPa · s or more, and further preferably 3 mPa · s or more. The upper limit is more preferably 50 mPa · s or less, further preferably 30 mPa · s or less, and particularly preferably 15 mPa · s or less.

The container for the composition of the present invention is not particularly limited, and a known container can be used. Moreover, as a container, for the purpose of suppressing impurities from being mixed into raw materials and compositions, a multilayer bottle in which the inner wall of the container is composed of six types and six layers of resin, and a bottle having six types of resin and a seven layer structure are used. It is also preferable to use it. Examples of such a container include a container described in JP-A-2015-123351.

The composition of the present invention can be preferably used as a composition for forming an infrared transmission filter.

<Method for preparing composition>
The composition of the present invention can be prepared by mixing the aforementioned components. In preparing the composition, the composition may be prepared by dissolving or dispersing all the components in the solvent at the same time. If necessary, two or more solutions or dispersions appropriately blending each component may be prepared in advance. They may be prepared and mixed to prepare a composition at the time of use (at the time of application).

In addition, the preparation of the composition preferably includes a process of dispersing the pigment. In the process of dispersing the pigment, the mechanical force used for dispersing the pigment includes compression, squeezing, impact, shearing, cavitation and the like. Specific examples of means for carrying out these processes include a bead mill, a sand mill, a roll mill, a ball mill, a paint shaker, a microfluidizer, a high-speed impeller, a sand grinder, a flow jet mixer, a high-pressure wet atomization, and an ultrasonic dispersion. It is done. Further, in the pulverization of the pigment in the sand mill (bead mill), it is preferable to use the beads having a small diameter, and to perform the treatment under the condition that the pulverization efficiency is increased by increasing the filling rate of the beads. Further, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment. Also, regarding the process and disperser for dispersing pigments, “Dispersion Technology Encyclopedia, Issued by Information Technology Corporation, July 15, 2005”, “Dispersion technology centering on suspension (solid / liquid dispersion system) and industrial The process and the disperser described in Paragraph No. 0022 of Japanese Patent Application Laid-Open No. 2015-157893 can be used. In the process of dispersing the pigment, the pigment may be refined in a salt milling process. For the materials, equipment, processing conditions, etc. used in the salt milling process, for example, descriptions in JP-A Nos. 2015-194521 and 2012-046629 can be referred to.

In preparing the composition, it is preferable to filter the composition with a filter for the purpose of removing foreign substances and reducing defects. Any filter can be used without particular limitation as long as it is a filter that has been conventionally used for filtration. For example, fluororesin such as polytetrafluoroethylene (PTFE), polyamide resin such as nylon (eg nylon-6, nylon-6,6), polyolefin resin such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight) And a filter using a material such as polyolefin resin). Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.

The pore size of the filter is preferably from 0.01 to 7.0 μm, more preferably from 0.01 to 3.0 μm, still more preferably from 0.05 to 0.5 μm. If the hole diameter of a filter is the said range, a fine foreign material can be removed more reliably. The filter manufacturer's nominal value can be referred to for the filter pore size value. Various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (former Nihon Microlith Co., Ltd.), KITZ Microfilter Co., Ltd., etc. can be used.

It is also preferable to use a fiber-like filter medium as the filter. Examples of the fiber-shaped filter medium include polypropylene fiber, nylon fiber, and glass fiber. Examples of commercially available products include SBP type series (such as SBP008), TPR type series (such as TPR002 and TPR005), and SHPX type series (such as SHPX003) manufactured by Loki Techno.

When using filters, different filters (for example, a first filter and a second filter) may be combined. In that case, filtration with each filter may be performed only once or may be performed twice or more. Moreover, you may combine the filter of a different hole diameter within the range mentioned above. Moreover, filtration with a 1st filter may be performed only with respect to a dispersion liquid, and after mixing other components, it may filter with a 2nd filter.

<Membrane>
Next, the film of the present invention will be described. The film of the present invention is obtained from the above-described composition of the present invention. The film of the present invention can be preferably used as an infrared transmission filter.

In the film of the present invention, the transmittance of light having a wavelength of 700 nm is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less. Moreover, it is preferable that the transmittance | permeability of the light of wavelength 810nm is 70% or more, It is more preferable that it is 75% or more, It is still more preferable that it is 80% or more. Further, the maximum value of the transmittance of light having a wavelength of 400 to 700 nm is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less. Further, the minimum transmittance of light having a wavelength of 810 to 1100 nm is preferably 70% or more, more preferably 75% or more, and further preferably 80% or more.

The film thickness of the film of the present invention can be appropriately adjusted according to the purpose. 10.0 μm or less is preferable, 5.0 μm or less is more preferable, 3.0 μm or less is further preferable, 2.5 μm or less is even more preferable, 2.0 μm or less is even more preferable, and 1.5 μm or less is particularly preferable. The lower limit of the film thickness is preferably 0.4 μm or more, more preferably 0.5 μm or more, still more preferably 0.6 μm or more, still more preferably 0.7 μm or more, still more preferably 0.8 μm or more, and 0.9 μm. The above is particularly preferable.

<Method for producing membrane>
Next, the manufacturing method of the film | membrane of this invention is demonstrated. The film | membrane of this invention can be manufactured through the process of apply | coating the composition of this invention.

In the method for producing a film of the present invention, the composition is preferably coated on a support. Examples of the support include a substrate made of a material such as silicon, alkali-free glass, soda glass, Pyrex (registered trademark) glass, or quartz glass. These substrates may be formed with an organic film or an inorganic film. As a material of the organic film, for example, the resin described in the column of the composition described above can be given. Moreover, the board | substrate comprised with resin can also be used for a support body. The support may be formed with a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like. The support may be formed with a black matrix that isolates each pixel. In addition, the support may be provided with an undercoat layer for improving adhesion to the upper layer, preventing diffusion of substances, or flattening the substrate surface, if necessary. In the case where a glass substrate is used as the support, it is preferable to use an inorganic film formed on the glass substrate or dealkalized on the glass substrate.

As a method for applying the composition, a known method can be used. For example, a dropping method (drop casting); a slit coating method; a spray method; a roll coating method; a spin coating method (spin coating method); a casting coating method; a slit and spin method; a pre-wet method (for example, JP 2009-145395 A). The method described in the publication No.); inkjet (for example, on-demand method, piezo method, thermal method), ejection printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Various printing methods; transfer method using a mold or the like; nanoimprint method. The application method by ink jet is not particularly limited. For example, the method described in “Expanding and usable ink jet-unlimited possibilities seen in patents, published in February 2005, Sumibe Techno Research” (particularly, 115 to 133). Page), JP 2003-262716 A, JP 2003-185831 A, JP 2003-261827 A, JP 2012-126830 A, JP 2006-169325 A, and the like. It is done. The application by spin coating is preferably performed at a rotational speed of 1000 to 2000 rpm. As for coating by spin coating, as described in JP-A-10-142603, JP-A-11-302413, JP-A-2000-157922, the rotational speed is increased during coating. Also good. In addition, the spin coating process described in “Chemicals and Processes for Cutting-edge Color Filters”, January 31, 2006, can be suitably used. Moreover, about the coating method of a composition, the method as described in international publication WO2017 / 030174 and international publication WO2017 / 018419 is mentioned, The content of these is integrated in this specification.

The composition layer (coating film) formed by applying the composition may be dried (pre-baked). When a film is manufactured by a low temperature process, pre-baking may not be performed. When prebaking is performed, the prebaking temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and even more preferably 110 ° C. or lower. For example, the lower limit may be 50 ° C. or higher, and may be 80 ° C. or higher. The pre-bake time is preferably 10 seconds to 3000 seconds, more preferably 40 to 2500 seconds, and further preferably 80 to 220 seconds. Pre-baking can be performed using a hot plate, an oven, or the like.

The film production method preferably further includes a step of forming a pattern. Examples of the pattern forming method include a pattern forming method using a photolithography method and a pattern forming method using a dry etching method, and a pattern forming method using a photolithography method is preferable. Note that in the case where the film of the present invention is used as a flat film, a step of forming a pattern may not be performed. Hereinafter, the process of forming a pattern will be described in detail.

(When forming a pattern by photolithography)
The pattern forming method by the photolithography method includes a step of exposing the composition layer formed by applying the composition of the present invention (exposure step), and developing and removing the composition layer in the unexposed area. And a step of forming a pattern (development step). If necessary, a step of baking the developed pattern (post-bake step) may be provided. Hereinafter, each step will be described.

<< Exposure process >>
In the exposure step, the composition layer is exposed in a pattern. For example, pattern exposure can be performed by exposing the composition layer through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. Thereby, an exposed part can be hardened. Examples of radiation (light) that can be used for exposure include g-line and i-line. Further, light having a wavelength of 300 nm or less (preferably light having a wavelength of 180 to 300 nm) can be used. Examples of the light having a wavelength of 300 nm or less include KrF rays (wavelength 248 nm), ArF rays (wavelength 193 nm), and KrF rays (wavelength 248 nm) are preferable. Irradiation dose (exposure dose), for example, preferably 0.03 ~ 2.5J / cm ^2, more preferably 0.05 ~ 1.0J / cm ^2, most preferably 0.08 ~ 0.5J / cm ² . The oxygen concentration at the time of exposure can be appropriately selected. For example, exposure may be performed in the air, exposure may be performed in a low oxygen atmosphere (for example, 15% by volume, 5% by volume, substantially oxygen-free) with an oxygen concentration of 19% by volume or less. You may expose in 21 degree% high oxygen atmosphere (for example, 22 volume%, 30 volume%, 50 volume%). The exposure illuminance can be appropriately set, and is preferably selected from the range of 1000 to 100,000 W / m ² . Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m ² at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m ^2.

<< Development process >>
Next, a pattern is formed by developing and removing the unexposed composition layer in the exposed composition layer. The development removal of the composition layer in the unexposed area can be performed using a developer. Thereby, the composition layer of the unexposed part in an exposure process elutes in a developing solution, and only the photocured part remains on a support body. The temperature of the developer is preferably 20 to 30 ° C., for example. The development time is preferably 20 to 180 seconds. Moreover, in order to improve residue removability, the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.

The developer is preferably an alkaline aqueous solution obtained by diluting an alkaline agent with pure water. Examples of the alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide. Organic compounds such as ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene Alkaline compounds, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate Um, and inorganic alkaline compound such as sodium metasilicate. As the alkaline agent, a compound having a large molecular weight is preferable in terms of environment and safety. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. Further, the developer may further contain a surfactant. As surfactant, the surfactant mentioned above is mentioned, A nonionic surfactant is preferable. The developer may be once manufactured as a concentrated solution and diluted to a necessary concentration at the time of use from the viewpoint of convenience of transportation and storage. The dilution factor is not particularly limited, but can be set, for example, in the range of 1.5 to 100 times. In addition, when alkaline aqueous solution is used as a developing solution, it is preferable to wash | clean (rinse) with a pure water after image development. The rinsing is preferably performed by supplying a rinsing liquid to the composition layer after development while rotating the support on which the composition layer after development is formed. It is also preferable to move the nozzle for discharging the rinsing liquid from the center of the support to the periphery of the support. At this time, when moving from the central part of the support body of the nozzle to the peripheral part, the nozzle may be moved while gradually decreasing the moving speed of the nozzle. By performing rinsing in this manner, in-plane variation of rinsing can be suppressed. Further, the same effect can be obtained by gradually decreasing the rotational speed of the support while moving the nozzle from the center of the support to the peripheral edge.

Developed, dried and then heat-treated (post-baked). Post-baking is a heat treatment after development for complete film curing. In the case of performing post-baking, the post-baking temperature is preferably 100 to 240 ° C. From the viewpoint of film curing, 200 to 230 ° C. is more preferable. Post-baking is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so that the developed film has the above temperature conditions. It can be carried out.

(When pattern is formed by dry etching method)
Pattern formation by the dry etching method is a method in which a composition layer formed by applying the composition of the present invention on a support is cured to form a cured product layer, and then a resist patterned on the cured product layer is formed. The layer can be formed, and then the patterned resist layer can be used as a mask to dry-etch the cured product layer using an etching gas. Regarding the pattern formation by the dry etching method, the description in paragraphs 0010 to 0067 of JP2013-064993A can be referred to, and the contents thereof are incorporated in this specification.

<Infrared transmission filter>
Next, the infrared transmission filter of the present invention will be described. The infrared transmission filter of the present invention has the above-described film of the present invention.

The infrared transmission filter of the present invention can be used in combination with a color filter containing a chromatic colorant. A color filter can be manufactured using the coloring composition containing a chromatic colorant. The coloring composition can further contain a curable compound, a resin, a photopolymerization initiator, a surfactant, a solvent, a polymerization inhibitor, an ultraviolet absorber, and the like. Moreover, the aspect which has the pixel of the film | membrane of this invention and the pixel chosen from red, green, blue, magenta, yellow, cyan, black, and colorless is also a preferable aspect.

<Solid-state imaging device>
The solid-state imaging device of the present invention has the above-described infrared transmission filter of the present invention. The configuration of the solid-state imaging device is not particularly limited as long as it is a configuration having the film of the present invention and functions as a solid-state imaging device. For example, the following configurations can be mentioned.

On the support, a transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of the solid-state imaging device, and a light shielding film made of tungsten or the like that opens only the light receiving part of the photodiode on the photodiode and the transfer electrode, The device has a device protective film made of silicon nitride or the like formed on the light shielding film so as to cover the entire surface of the light shielding film and the photodiode light receiving portion, and an infrared transmission filter on the device protective film. Further, the device has a condensing means (for example, a microlens, etc., the same shall apply hereinafter) on the device protective film and below the infrared transmitting filter (on the side close to the support), or a condensing means on the infrared transmitting filter. It may have a configuration or the like. Further, the infrared transmission filter may have a structure in which a film forming each pixel of the infrared transmission filter is embedded in a space partitioned by a partition, for example, in a lattice shape. In this case, the partition wall preferably has a lower refractive index than each pixel. Examples of the image pickup apparatus having such a structure include apparatuses described in JP 2012-227478 A and JP 2014-179577 A.

The solid-state imaging device of the present invention preferably has a band-pass filter on the optical path of the infrared transmission filter. Examples of the bandpass filter include a dielectric multilayer film. The dielectric multilayer film is a film that shields infrared rays by utilizing the effect of light interference. The dielectric multilayer film can be produced by alternately laminating a plurality of high-refractive-index dielectric thin films (high-refractive-index material layers) and low-refractive-index dielectric thin films (low-refractive-index material layers). . The number of laminated dielectric thin films in the dielectric multilayer film is preferably 2 to 100 layers, more preferably 4 to 60 layers, and even more preferably 6 to 40 layers.

As a material used for forming the high refractive index material layer, a material having a refractive index of 1.7 to 2.5 is preferable. Specific examples include Sb ₂ O ₃ , Sb ₂ S ₃ , Bi ₂ O ₃ , CeO ₂ , CeF ₃ , HfO ₂ , La ₂ O ₃ , Nd ₂ O ₃ , Pr ₆ O ₁₁ , Sc ₂ O ₃ , SiO , Ta ₂ O ₅ , TiO ₂ , TlCl, Y ₂ O ₃ , ZnSe, ZnS, ZrO _{2 and the} like. The material used for forming the low refractive index material layer is preferably a material having a refractive index of 1.2 to 1.6. Specific examples include Al ₂ O ₃ , BiF ₃ , CaF ₂ , LaF ₃ , PbCl ₂ , PbF ₂ , LiF, MgF ₂ , MgO, NdF ₃ , SiO ₂ , Si ₂ O ₃ , NaF, ThO ₂ , ThF _4. Na ₃ AlF _{6 and the} like.

The method for forming the dielectric multilayer film is not particularly limited. For example, a vacuum vapor deposition method such as ion plating or ion beam, a physical vapor deposition method (PVD method) such as sputtering, a chemical vapor deposition method ( CVD method).

The thickness of each of the high refractive index material layer and the low refractive index material layer is preferably 0.1λ to 0.5λ of the infrared wavelength λ (nm) to be blocked. By setting the thickness within the above range, it is easy to control blocking / transmission of a specific wavelength.

The band-pass filter may be provided on the light incident side to the infrared transmission filter, or may be provided on the light emission side from the infrared transmission filter. The bandpass filter may be in contact with the infrared transmission filter, and another layer may be interposed between the bandpass filter and the infrared transmission filter.

It is preferable that the band-pass filter has a band-pass filter that transmits at least a part of the infrared light transmitted by the infrared transmission filter. According to this aspect, the solid-state image sensor can receive infrared light with less noise, and the sensor sensitivity of the solid-state image sensor can be increased. The band-pass filter is preferably a filter that transmits visible light and at least part of infrared rays that are transmitted by the infrared transmission filter. In particular, in the case where the solid-state imaging device of the present invention further includes a color filter in addition to the infrared transmission filter, the bandpass filter is a filter that transmits visible light and at least a part of infrared rays transmitted by the infrared transmission filter. Preferably there is.

The bandpass filter has a maximum transmittance of 10% or less (preferably 7% or less, more preferably 5% or less) in the wavelength range of 730 to 780 nm, and a minimum transmittance value in the wavelength range of 840 to 860 nm. Is preferably 70% or more (preferably 80% or more, more preferably 90% or more).
The bandpass filter preferably has a minimum transmittance of 70% or more (preferably 80% or more, more preferably 90% or more) in the wavelength range of 400 to 700 nm.
The bandpass filter preferably has a maximum transmittance of 10% or less (preferably 7% or less, more preferably 5% or less) in the wavelength range of 900 to 1200 nm.

Favorable combinations of infrared transmission filters and bandpass filters include the following combinations. In the wavelength range of 700 to 850 nm, the wavelength λ1 at which the transmittance of the infrared transmission filter is 50% is shorter than the shortest wavelength λ2 at which the transmittance of the bandpass filter is 50%, and the wavelength λ2 and the wavelength λ1 In which the difference is 30 nm or more. The wavelength λ1 is preferably 700 to 800 nm, more preferably 720 to 780 nm. The wavelength λ2 is preferably 770 to 840 nm, and more preferably 790 to 835 nm.

As an embodiment of a solid-state imaging device having an infrared transmission filter and a color filter, there is a solid-state imaging device having a structure shown in FIG. In FIG. 1, a near-infrared cut filter 111 and an infrared transmission filter 114 are arranged on the imaging region 110 of the solid-state imaging device. A color filter 112 is laminated on the near infrared cut filter 111. A micro lens 115 is disposed on the incident light hν side of the color filter 112 and the infrared transmission filter 114. A planarization layer 116 is formed so as to cover the microlens 115.

The spectral characteristic of the near-infrared cut filter 111 is selected according to the emission wavelength of the infrared light-emitting diode (infrared LED) to be used. The color filter 112 is a color filter in which pixels that transmit and absorb light of a specific wavelength in the visible region are formed, and is not particularly limited. A conventionally known color filter for pixel formation can be used. For example, a color filter in which red (R), green (G), and blue (B) pixels are formed is used. For example, the description of paragraph numbers 0214 to 0263 in Japanese Patent Application Laid-Open No. 2014-043556 can be referred to, and the contents thereof are incorporated in the present specification. The infrared transmission filter 114 is the infrared transmission filter of the present invention.

In the infrared sensor shown in FIG. 1, it is also preferable that a band pass filter is provided on the optical path of the infrared transmission filter 114. The band pass filter may be provided on the light incident side to the infrared transmission filter 114 or may be provided on the light emission side from the infrared transmission filter 114. The band pass filter may be in contact with the infrared transmission filter 114, and the band pass filter may have another layer interposed between the infrared transmission filter 114.

The solid-state imaging device of the present invention can be used by being incorporated in an image display device (for example, a liquid crystal display device or an organic electroluminescence (organic EL) display device). The solid-state imaging device of the present invention is for iris authentication, distance measurement, proximity sensor, gesture sensor, motion sensor, TOF (Time-of-Flight) sensor, vein sensor, blood vessel visualization, sebum It can be preferably used for applications such as quantity measurement, fluorescent labeling, and surveillance camera.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Unless otherwise specified, “part” is based on mass.

<Measurement of weight average molecular weight>
The weight average molecular weight of the resin was measured by gel permeation chromatography (GPC) according to the following conditions.
Column type: TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000 and TOSOH TSKgel Super HZ2000 connected column Developing solvent: Tetrahydrofuran Column temperature: 40 ° C
Flow rate (sample injection amount): 1.0 μL (sample concentration 0.1% by mass)
Device name: HLC-8220GPC manufactured by Tosoh Corporation
Detector: RI (refractive index) detector Calibration curve base resin: Polystyrene resin

<Manufacture of metal azo pigments>
(Production of metal azo pigment 1)
46.2 g of diazobarbituric acid and 38.4 g of barbituric acid were added into 1100 g of distilled water at 85 ° C. Next, an aqueous potassium hydroxide solution was added to this solution to adjust the pH to about 5, and then stirred for 90 minutes to produce an azobarbituric acid precursor.
Next, 1500 g of distilled water at 82 ° C. was added to the azobarbituric acid precursor. Then 10 g of 30% hydrochloric acid was added dropwise. Then 79.4 g melamine was added. A mixture of 0.282 moles of about 25% zinc chloride solution and 0.0015 moles of about 30% copper (II) chloride solution was then added dropwise. Next, the solution to which these were added was held at a temperature of 82 ° C. for 3 hours, and then KOH was added to adjust the pH to about 5.5. Subsequently, the temperature of this solution was raised to 90 ° C., and diluted by adding 100 g of distilled water while maintaining the temperature of 90 ° C. Next, 21 g of 30% hydrochloric acid was added dropwise to the solution, and then heat-treated at a temperature of 90 ° C. for 12 hours. Next, an aqueous potassium hydroxide solution was added to the solution after the heat treatment to adjust the pH to about 5. The pigment was then isolated from this solution on a suction filter, washed, dried in a vacuum drying cabinet at 80 ° C., and then ground in a standard laboratory mill for about 2 minutes to produce metal azo pigment 1.

<Method for distilling off environmentally restricted substances>
(Production Example 1) Production of polymerizable monomer D3 In a flask, 50 g of polyfunctional acrylate (KAYARAD DPHA, Nippon Kayaku Co., Ltd.) containing 238 ppm by mass of toluene as a residual solvent, and propylene glycol monomethyl acetate (PGMEA) And 80 mg of 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) were added, the external temperature was set to 90 ° C., and the pressure inside the flask was gradually reduced from normal pressure. The pressure was reduced to 68 mmHg and distilled off under reduced pressure over 4 hours. Thereafter, the weight in the system was adjusted with PGMEA so as to be 100 g to obtain a polyfunctional acrylate solution 1 (polymerizable monomer D3). When the amount of residual solvent (toluene) contained in the polyfunctional acrylate solution 1 was measured by gas chromatography, it was confirmed that the amount was reduced to 11 mass ppm. In addition, a peak derived from a polyfunctional acrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) was detected by ¹ H-NMR (nuclear magnetic resonance), and it was confirmed that no crosslinking reaction due to radical polymerization occurred.

(Production Example 2) Production of Dispersant C5 50 g of an acrylate compound (Aronix M-5300, manufactured by Toagosei Co., Ltd.) containing 835 mass ppm of toluene as a residual solvent in the flask, 50 g of PGMEA, and 40 mg of TEMPO, The external temperature was set to 90 ° C., and the pressure inside the flask was gradually reduced from normal pressure to 66 mmHg, and distilled off under reduced pressure over 4 hours. Thereafter, the weight in the system was adjusted with PGMEA so as to be 100 g, and a monomer solution 1 was obtained. When the amount of residual solvent (toluene) contained in the monomer solution 1 was measured by gas chromatography, it was confirmed that the amount was reduced to 9 ppm by mass. In addition, a peak derived from an acrylate compound (Aronix M-5300, manufactured by Toagosei Co., Ltd.) was detected by ¹ H-NMR, and it was confirmed that a crosslinking reaction due to radical polymerization did not occur.

Into a three-necked flask, 1044.2 g of ε-caprolactone, 184.3 g of δ-valerolactone, and 71.6 g of 2-ethyl-1-hexanol were introduced to obtain a mixture. Next, the above mixture was stirred while blowing nitrogen. Next, 0.61 g of monobutyltin oxide was added to the mixture and the resulting mixture was heated to 90 ° C. After 6 hours, ¹ H-NMR was used to confirm the disappearance of the signal derived from 2-ethyl-1-hexanol in the mixture, and then the mixture was heated to 110 ° C. After continuing the polymerization reaction at 110 ° C. for 12 hours under nitrogen, the disappearance of signals derived from ε-caprolactone and δ-valerolactone was confirmed by ¹ H-NMR, and the molecular weight of the obtained compound was determined by GPC method. Measurements were made. After confirming that the molecular weight of the compound reached the desired value, 0.35 g of 2,6-di-tert-butyl-4-methylphenol was added to the mixture containing the above compound, and then further obtained. To this mixture, 87.0 g of 2-methacryloyloxyethyl isocyanate was added dropwise over 30 minutes. Six hours after the completion of the dropping, ¹ H-NMR confirmed that the signal derived from 2-methacryloyloxyethyl isocyanate (MOI) had disappeared. Then, 1387.0 g of PGMEA was added to the mixture, and the concentration was 50 mass. 2770 g of a% macromonomer A-1 solution was obtained. The structure of macromonomer A-1 (shown in formula (A-1)) was confirmed by ¹ H-NMR. The resulting macromonomer A-1 had a weight average molecular weight of 6,000.

To the three-necked flask, 120 g of the macromonomer A-1 solution, 280 g of the monomer solution 1 and 266.7 g of PGMEA were added to obtain a mixture. The mixture was stirred while blowing nitrogen. Next, the temperature of the mixture was raised to 75 ° C. while flowing nitrogen into the flask. Next, 1.65 g of dodecyl mercaptan and 0.83 g of 2,2′-azobis (methyl 2-methylpropionate) (hereinafter also referred to as “V-601”) are added to the mixture, and a polymerization reaction is performed. Started. After the mixture was heated at 75 ° C. for 2 hours, an additional 0.83 g of V-601 was added to the mixture. After 2 hours, an additional 0.83 g of V-601 was added to the mixture. After further reaction for 2 hours, the mixture was heated to 90 ° C. and stirred for 3 hours. The polymerization reaction was completed by the above operation.
After completion of the reaction, 6.0 g of dimethyldodecylamine and 2.46 g of TEMPO were added under air, and then 15.7 g of glycidyl methacrylate was added. After continuing the reaction at 90 ° C. for 24 hours under air, the completion of the reaction was confirmed by acid value measurement. After cooling to 60 ° C., 15.6 g of 2-isocyanatoethyl acrylate (AOI) was further added to the resulting mixture and reacted at 60 ° C. for 6 hours. The disappearance of AOI was confirmed by ¹ H-NMR measurement. An appropriate amount of PGMEA was added to the resulting mixture to obtain a 20% by mass solution of Dispersant C-5. The obtained resin C-5 had a weight average molecular weight of 25,000, an acid value of 80 mgKOH / mg, and a C = C value of 0.9 mmol / g. Further, when the amount of toluene contained in the resin C-5 was measured, it was confirmed that it was 5 ppm by mass or less.

[Test Example 1]
<Manufacture of pigment dispersion>
After mixing the raw materials listed in Table 1 below, add 230 parts by mass of zirconia beads having a diameter of 0.3 mm, perform a dispersion treatment for 5 hours using a paint shaker, separate the beads by filtration, and obtain a pigment dispersion. Manufactured. The numerical values described in the table below are parts by mass.

<Preparation of composition>
The compositions shown in Table 2 below were mixed to prepare compositions of Examples 1 to 8 and Comparative Examples 1 and 2. The numerical values described in the table below are parts by mass.

The raw materials described in the above table are as follows.

(Color material)
Metal azo pigment 1: metal azo pigment 1 described above
PR254: C.I. I. Pigment Red 254 (red colorant)
PR264: C.I. I. Pigment Red 264 (red colorant)
PY139: C.I. I. Pigment Yellow 139 (Yellow colorant)
PV23: C.I. I. Pigment Violet 23 (purple colorant)
PB16: C.I. I. Pigment Blue 16 (metal-free phthalocyanine compound)
IB: Irgaphor Black (BASF, black colorant)
PBk32: C.I. I. Pigment Black 32 (black colorant)
K1: Compound having the following structure (black colorant)

(Pigment derivative)
B1: Compound having the following structure.

(Dispersant)
C1: Resin having the following structure (the numerical value attached to the main chain is a molar ratio, and the numerical value attached to the side chain is the number of repeating units. Mw = 20,000)
C2: Resin having the following structure (the numerical value attached to the main chain is a molar ratio, and the numerical value attached to the side chain is the number of repeating units. Mw = 24,000)
C5: Dispersant C5 produced in Production Example 2 described above (solid content concentration 20% by mass)
C6: Copolymer described in Example 1 of International Publication WO2012 / 001945 (solid content 20% by mass)

(resin)
P1: Resin having the following structure (Mw = 11000, the numerical values attached to the main chain are molar ratios, Me is a methyl group)
P2: Resin having the following structure. (Mw = 4400, acid value = 95 mgKOH / g, in the following structural formula, M is a phenyl group, and A is a biphenyltetracarboxylic anhydride residue.)
P3: Cyclomer ACA250 (solid content concentration 45% by mass, manufactured by Daicel Corporation)
P4: Resin having the following structure (Mw = 30000, the numerical values attached to the main chain are molar ratios)

(Polymerizable monomer)
D1: TMPEOTA (manufactured by Daicel Ornex Co., Ltd.)
D2: Compound having the following structure

D3: polymerizable monomer D3 produced in Production Example 1 (solid content concentration 50% by mass)
D4: Aronix M-520 (manufactured by Toagosei Co., Ltd.)

(Silane coupling agent)
H1: Compound having the following structure (Et is an ethyl group in the following structural formula)

(Photopolymerization initiator)
I1 to I4: Compounds having the following structures (oxime compounds)

I5: Adeka Arcles NCI-831 (manufactured by ADEKA, oxime compound)
I6: Compound NO. Described in paragraph No. 0007 of JP-T-2017-523465. 12
I7: Compound of formula (2) described in paragraph No. 0025 of JP-A No. 2017-151342 I8: Compound 6 described in paragraph No. 0031 of JP-A No. 2017-167399
(UV absorber)
L1: Compound having the following structure

(Multifunctional thiol)
M1: Trimethylolpropane tris (3-mercaptobutyrate)

(Surfactant)
F1: The following mixture (Mw = 14000). In the following formula,% indicating the ratio of repeating units is mol%.

(Epoxy compound)
N1: EHPE3150 (manufactured by Daicel Corporation)
(Polymerization inhibitor)
G1: p-methoxyphenol (solvent)
J1: Propylene glycol monomethyl ether acetate (PGMEA)
J2: Cyclohexanone

<Evaluation of spectral characteristics>
Each composition was applied on a glass substrate using a spin coater after adjusting the number of revolutions so that the film thickness after post-baking was the film thickness described in the following table, and 120 ° C. using a hot plate at 100 ° C. Pre-baked for 2 seconds. Next, the entire surface of the pre-baked coating film was exposed by irradiating i-line with an exposure amount of 1000 mJ / cm ² , and then post-baked at 220 ° C. for 5 minutes using a hot plate to form a film.
Using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation), the absorbance and transmittance of the obtained film at a wavelength of 400 to 1100 nm were measured, and the absorbance A at a wavelength of 700 nm and the transmittance at a wavelength of 700 nm were measured. TA, absorbance B at a wavelength of 810 nm, transmittance TB at a wavelength of 810 nm, minimum value C of absorbance at a wavelength range of 400 to 700 nm, maximum value TC of transmittance at a wavelength range of 400 to 700 nm, absorbance at a wavelength range of 810 to 1100 nm Maximum value D, minimum value TD of transmittance in the wavelength range of 810 to 1100 nm, ratio A / B of absorbance A at wavelength 700 nm to absorbance B at wavelength 810 nm, minimum value C of absorbance in the range of wavelength 400 to 700 nm And absorbance in the wavelength range of 810 to 1100 nm The ratio C / D of the maximum value D were measured.

<Evaluation of light resistance>
Each composition was applied on soda glass (75 mm × 75 mm square, thickness 1.1 mm) using a spin coater with the rotation speed adjusted so that the film thickness after post-baking was 1.1 μm, It prebaked for 120 seconds using a 100 degreeC hotplate. Next, the entire surface of the pre-baked coating film was exposed at an exposure amount of 1000 mJ / cm ² using an ultrahigh pressure mercury lamp (“USH-500BY” (trade name)) manufactured by USHIO INC. Subsequently, the exposed coating film was post-baked at 220 ° C. for 5 minutes using a hot plate in an air atmosphere to form a film. With respect to the obtained film, transmittance in the range of 400 nm to 700 nm was measured using “MCPD-3000” (trade name) manufactured by Otsuka Electronics Co., Ltd.
Next, an ultraviolet cut filter (KU-1000100 [trade name] manufactured by ASONE Co., Ltd.) is attached to this film, and 100,000 lux is used using a light resistance tester (Xenon Weather Meter SX75 [trade name] manufactured by Suga Test Instruments Co., Ltd.). Was irradiated for 100 hours (total 10 million luxh), and a light resistance test was conducted. The temperature of the film during the light resistance test (temperature in the test apparatus) was set to 63 ° C. The relative humidity in the test apparatus was 50%. After the light resistance test, the amount of change in the transmittance of the film was measured to evaluate the light resistance. Note that the amount of change in transmittance compared is the amount of change for the wavelength with the largest amount of change in transmittance in the wavelength range of 400 nm to 700 nm (| transmittance before light resistance test (%) − after light resistance test). Transmittance (%) |). The smaller the numerical value of the change in transmittance, the better the light resistance.
3: The amount of change is 3% or less 2: The amount of change exceeds 3%, 6% or less 1: The amount of change exceeds 6%.

As shown in the above table, the film obtained using the composition of the example was superior in light resistance to the film obtained using the composition of the comparative example.

[Test Example 2]
(Example 101)
An 8-inch (20.32 cm) silicon wafer was used as the support. On the support, CT-4000L (manufactured by FUJIFILM Electromaterials Co., Ltd.) is uniformly applied by spin coating to form a coating film, and the formed coating film is heated in an oven at 220 ° C. for 1 hour. The coating film was cured to form an undercoat layer. The spin coating speed was adjusted so that the thickness of the coating film after the heat treatment was about 0.1 μm.
Next, the composition of Example 1 was applied on the undercoat layer of the above support using a spin coater so that the film thickness after post-baking was 1.1 μm, and at 100 ° C. using a hot plate. Dry for 120 seconds.
Next, using an i-line stepper exposure apparatus FPA-i5 + (manufactured by Canon Inc.), light having a wavelength of 365 nm is passed through the coating film through a mask having an island pattern of 100 μm square, and exposure of 1000 mJ / cm ² is performed. Irradiated in quantity. After the exposure, development was performed using an alkali developer (CD-2000, manufactured by FUJIFILM Electronics Materials Co., Ltd.) at 25 ° C. for 40 seconds. Thereafter, the substrate was rinsed with running water for 30 seconds, spin-dried, and then baked at 220 ° C. for 5 minutes using a hot plate to form an infrared transmission filter. A bandpass filter was formed on the surface of the obtained infrared transmission filter by the following method to produce a laminate of the infrared transmission filter and the bandpass filter. This laminate was incorporated into a solid-state image sensor according to a known method. The obtained solid-state imaging device was irradiated with light from an infrared light emitting diode (infrared LED) light source in a low illuminance environment (0.001 Lux), and an image was captured to evaluate the image performance. The subject was clearly recognized on the image.

The bandpass filter was manufactured as follows.
A silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer were alternately laminated at a deposition temperature of 100 ° C. to obtain a bandpass filter.
This bandpass filter had a maximum transmittance of 10% or less in the wavelength range of 730 to 780 nm and a minimum transmittance of 70% or more in the wavelength range of 840 to 860 nm. In the wavelength range of 700 to 850 nm, the wavelength λ1 at which the transmittance of the infrared transmission filter is 50% is shorter than the shortest wavelength λ2 at which the transmittance of the bandpass filter is 50%, and the wavelength λ2 and the wavelength The difference from λ1 was 30 nm or more.

110: imaging region, 111: near-infrared cut filter, 112: color filter, 114: infrared transmission filter, 115: microlens, 116: flattening layer

Claims

A composition comprising a metal-free phthalocyanine compound, a red colorant, and a solvent, and a ratio A / B of absorbance A at a wavelength of 700 nm and absorbance B at a wavelength of 810 nm is 10 or more.
The composition according to claim 1, wherein the metal-free phthalocyanine compound is a blue colorant.
The composition according to claim 1 or 2, wherein the metal-free phthalocyanine compound is Color Index Pigment Blue 16.
The composition according to any one of claims 1 to 3, further comprising at least one selected from a yellow colorant and a purple colorant.
The ratio C / D of the minimum absorbance C in the wavelength range of 400 to 700 nm and the maximum absorbance D in the wavelength range of 810 to 1100 nm of the composition is 4.5 or more. The composition according to claim 1.
The composition according to any one of claims 1 to 5, which is used for an infrared transmission filter.
A film obtained using the composition according to any one of claims 1 to 6.
An infrared transmission filter having the film according to claim 7.
A solid-state imaging device having the infrared transmission filter according to claim 8.
The solid-state imaging device according to claim 9, further comprising: a band-pass filter that transmits at least part of infrared light transmitted by the infrared transmission filter on an optical path of the infrared transmission filter.
The solid-state imaging device according to claim 10, wherein the band-pass filter is a filter that transmits visible light and at least a part of infrared rays that the infrared transmission filter transmits.
12. The bandpass filter according to claim 10 or 11, wherein the maximum value of transmittance in the wavelength range of 730 to 780 nm is 10% or less, and the minimum value of transmittance in the wavelength range of 840 to 860 nm is 70% or more. The solid-state imaging device described.
In the wavelength range of 700 to 850 nm, the wavelength λ1 at which the transmittance of the infrared transmission filter is 50% is shorter than the shortest wavelength λ2 at which the transmittance of the bandpass filter is 50%, and the wavelength λ2 and the wavelength The solid-state imaging device according to any one of claims 10 to 12, wherein a difference from λ1 is 30 nm or more.